EP1450607A1 - Herbicidal composition - Google Patents

Herbicidal composition

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Publication number
EP1450607A1
EP1450607A1 EP02796559A EP02796559A EP1450607A1 EP 1450607 A1 EP1450607 A1 EP 1450607A1 EP 02796559 A EP02796559 A EP 02796559A EP 02796559 A EP02796559 A EP 02796559A EP 1450607 A1 EP1450607 A1 EP 1450607A1
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EP
European Patent Office
Prior art keywords
formula
compound
crc
alkoxy
alkyl
Prior art date
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Application number
EP02796559A
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German (de)
French (fr)
Inventor
Willy T. Rüegg
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Syngenta Participations AG
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Syngenta Participations AG
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Publication of EP1450607A1 publication Critical patent/EP1450607A1/en
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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2

Definitions

  • the present invention relates to a novel herbicidal composition comprising a herbicidal active ingredient combination that is suitable for the selective control of weeds in crops of useful plants, for example in crops of maize.
  • the invention relates also to a method of controlling weeds in crops of useful plants and to the use of the novel composition for that purpose.
  • p is 0 or 1 ;
  • R is a d-dalkylene, C 3 -C 6 alkenylene or C 3 -C 6 alkynylene chain, which may be substituted one or more times by halogen or by R 5 , the unsaturated bonds of the chain not being attached directly to the substituent X ⁇
  • X ! is oxygen, -O(CO)-, -(CO)O-, -O(CO)O-, -N(R 6 )-O-, -O-NR 51 -, thio, sulfinyl, sulfonyl,
  • R 2 is a C ⁇ -C 8 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl group, which is substituted one or more times by halogen, hydroxy, amino, formyl, nitro, cyano, mercapto, carbamoyl, C C 6 alkoxy,
  • R 2 is phenyl, which may be substituted one or more times by d-C 6 alkyl, CrC 6 haloalkyl, d-C 6 alkoxy, d-C 6 haloalkoxy, halogen, cyano, hydroxy or by nitro; or R 2 is C 3 -C 6 cycloalkyl; C 3 -C 6 cycloalkyl substituted by C C 6 alkoxy or by d-C 6 alkyl; 3-oxetanyl or 3-oxetanyl substituted by d-C 6 alkyl; or, when Q is Q 2 or Q 3 , or when Q is Q ⁇ wherein R 14 and R 22 denote a C 2 -C 3 alkylene chain, R 2 may additionally be a five- to ten-membered, monocyclic or fused bicyclic ring system, which may be aromatic, saturated or partially saturated and which may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur, the ring system being
  • Q is substituted by the group R 5 , or b) Q is the group Q 2 , or c) Q is the group Q 3 wherein X 1 is -O(CO)-, -(CO)O-, -N(R 6 )-O-, -O-NR 51 -, -SO 2 NR 7 -, -NR 52 SO 2 - or -NR 8 -; or d) Q is the group Q ⁇ wherein X is -N(R 6 )-O-, -O-NR 51 -, -SO 2 NR 7 -, -NR 52 SO 2 - or -NR 8 -, or e) Q is the group Qi wherein R 14 and R 22 in Qi denote a C 2 -C 3 alkylene chain and X ! is -O(CO)- or -(CO)O-;
  • R 3 is C C 3 haloalkyl
  • R 4 is hydrogen, halogen, d-C 3 alkyl, CrC 3 haloalkyl, C C 3 alkoxy, d-Csalkoxy-d-Csalkyl or d-C 3 alkoxy-CrC 3 alkoxy;
  • R 5 is hydroxy, d-C 6 alkoxy, C 3 -C 6 cycloalkyloxy, d-Cealkoxy-d-C ⁇ alkoxy, d-C 6 alkoxy-
  • R 6 , R 7 , R 8 , Rg, R 1 0, R 11 , R 12 , R5 1 and R 52 are each independently of the others hydrogen, d-C 6 alkyl, C C 6 haloalkyl, d-C 6 alkoxycarbonyl, CrC 6 alkylcarbonyl, C C ⁇ alkoxy-d-Cealkyl, d-Cealkoxy-d-C ⁇ alkyl substituted by CrC 6 alkoxy, benzyl, or phenyl, wherein phenyl and benzyl may in turn be substituted one or more times by d-C 6 alkyl, d-C 6 haloalkyl, d-C 6 - alkoxy, d-C- 6 haloalkoxy, halogen, cyano, hydroxy or by nitro; wherein R 6 is not hydrogen when R 9 is hydrogen, d-C 6 alkoxycarbonyl or d-C 6 alkylcarbonyl;
  • A! is C(R 14 R 15 ), NR 16 or oxygen
  • R 17 and R ⁇ 8 being each independently of the other C C 4 alkoxy, C C - alkylthio, CrC 4 aIkylsulfinyl or C ⁇ -C alkylsulfonyl; and that A 1 is other than NR 16 when A 2 is thio, sulfinyl or C(R 17 R 18 ), R 17 and R 18 being each independently of the other C C 4 alkoxy, d-C 4 alkylthio, C ⁇ -C alkylsulfinyl or C C 4 alkylsulfonyl;
  • Ru and R 22 are each independently of the other hydrogen, C ⁇ -C alkyl, C C 4 haloalkyl, C 3 -C 4 - alkenyl, C 3 -C 4 alkynyl, d-C 4 alkylthio, d-C 4 alkylsulfinyl, d-C 4 alkylsulfonyl, d-C 4 aIkylsulfonyl- oxy, d-C alkoxy, C ⁇ -C 4 alkoxycarbonyl or d-C 4 alkylcarbonyl;
  • R 15 and R 21 are each independently of the other hydrogen, d-C 4 alkyl, d-C 4 haloalkyl, C 3 -C 4 - alkenyl or C 3 -C 4 alkynyl;
  • R 17 is hydrogen, C ⁇ C ⁇ Ikyl, C C 4 haloalkyl, C ⁇ -C 4 alkoxy, C C 4 alkylthio, d-C 4 alkylsulfinyl or
  • R 18 is hydrogen, d-C 4 alkyl, C ⁇ -C 4 haIoalkyl, C 3 -C 4 alkenyl, C 3 -C 4 alkynyl, d-C 4 alkoxy, C C 4 - alkylthio, C C 4 alkylsulfinyl, d-C 4 alkylsulfonyl or di(d-C 4 )alkoxyalkyl-d-C 4 alkyl;
  • R 20 is d-C 4 alkyl, C 3 -C 6 cycloalkyl, C 3 -C 4 alkenyl, C 3 -C 4 alkynyl, d-C 4 alkylcarbonyl, C C 4 alkyl- carbonyloxy, di(C ⁇ -C 4 )alkylaminocarbonyl or benzyl, wherein the phenyl group may be substituted one or more times by CrCealkyl, d-C- 6 haloalkyl, CrC 6 alkoxy, C r C 6 haloalkoxy, halogen, cyano, hydroxy or by nitro;
  • R 19 and R 16 are each independently of the other hydrogen, d-C 4 alkyl, C 3 -C 6 cycloalkyl,
  • C 2 -C alkylene chain which may be interrupted by oxygen and/or by carbonyl and/or by sulfur, with the proviso that the oxygen and sulfur atoms are separated by at least one methylene group; or R i4 and R 8 together form a C 2 -C 4 alkylene chain; or
  • R 22 and R 18 together form a C 2 -C alkylene chain; or R 18 forms, together with R 22 or R 14 , a direct bond; or R 6 and R 18 together form a C 2 -C 4 alkylene chain;
  • R 13 is hydroxy; O " M + wherein M + is an alkali metal cation or an ammonium cation; halogen, d-C ⁇ 2 alkylsulfonyloxy, amino, d-C 4 alkylthio, d-C 12 alkylsulfinyl, CrC 12 alkylsulfonyl, d-C 12 - haloalkylthio, C C 12 haloalkylsulfinyl, d-C ⁇ 2 haloalkylsulfonyl, CrC 6 alkoxy-CrC 6 alkylthio,
  • R- I 3 is phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, phenylsulfonylamino, phenyl- sulfonyloxy or benzoyloxy, wherein the phenyl groups may in turn be substituted by one or more halogen, nitro, cyano, d-C 4 alkyl, C C 4 haloalkyl, CrC 4 alkoxy or d-C 4 haloalkoxy groups; or R 13 is a group Hetrthio, Het 2 -sulfinyl, Het 3 -sulfonyl, Het 4 -(CO)O or Het 5 -N(R 33 ); wherein
  • Het 1 ; Het 2 , Het 3 , Het 4 and Het 5 are each independently of the others a five- to ten- membered, monocyclic or fused bicyclic ring system, which may be aromatic or partially saturated and which may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur and wherein each ring system may contain no more than two oxygen atoms and no more than two sulfur atoms and the ring system may itself be substituted by d-C 6 alkyl, d-Cehaloalkyl, d-C 6 alkoxy, C C 6 haloalkoxy, C C 6 alkylthio, CrC 6 alkylsulfinyl, d-
  • R23, R2 , R 2 5, R 2 6, R27, R28, R29, R30 and R 33 are each independently of the others hydrogen or
  • R 23 and R 24 together or R 25 and R 26 together or R 27 and R 28 together or R 29 and R 30 together are pyrrolidino, piperidino, morpholino or thiomorpholino, each of which may be mono- or poly-substituted by methyl groups; or Q is Q 2
  • R 34 is hydrogen, d-C 4 alkyl, d-C 4 haloalkyl, C 3 -C 6 cycloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl or benzyl, wherein the phenyl group may be substituted one or more times by d-C 6 alkyl, d-C 6 haloalkyl, d-C 6 alkoxy, CrCehaloalkoxy, halogen, cyano, hydroxy or by nitro;
  • R 35 is hydrogen, d-dalkyl, d-dhaloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 4 alkenyl, C 3 -C 4 alkynyl or benzyl; wherein the phenyl group may be substituted one or more times by d-C 6 alkyl, d-C-ehaloalkyl, CrC 6 alkoxy, C C 6 haloalkoxy, halogen, cyano, hydroxy or by nitro;
  • R 36 is hydroxy; O " M + wherein M + is an alkali metal cation or an ammonium cation; halogen, d-C 12 alkylsulfonyloxy, amino, d-dalkylthio, CrC 12 alkylsulfinyl, d-d 2 alkylsulfonyl,
  • R 37 and R 38 together or R 39 and R 40 together or R 41 and R 42 together or R 43 and R ⁇ together are pyrrolidino, piperidino, morpholino or thiomorpholino, each of which may be mono- or poly-substituted by methyl groups; or Q is Q 3
  • R 49 is d-C 4 alkyl, d-C 4 haloalkyl, C 3 -C 6 cycloalkyl or halo-substituted C 3 -C 6 cycloalkyl;
  • R 50 is CrC 3 alkylene, which may be substituted by halogen, hydroxy, d-C 6 alkoxy, C 2 -C 6 - alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, d-C-ealkoxy-d-Cealkoxy, CrC 6 alkoxy-CrC 6 alkoxy- d-C 6 alkoxy, (3-oxetanyl)-oxy, or by (3-oxetanyl)-oxy substituted by CrC 6 alkyl, or by benzylthio, benzylsulfinyl, benzylsulfonyl, phenyl, phenoxy, phenylthio, phenylsulfinyl or by phenylsulfonyl, wherein the phenyl- and benzyl-containing groups may in turn be substituted by one or more d-C 6 alkyl, CrC
  • -R X ⁇ -R 2 is other than CrC 4 alkoxy-CrC 4 aIkoxy-d-C 4 alkyl when a) Q is Q T wherein A T is C(R ⁇ 4 R 15 ) and A 2 is C(R 17 R 18 ), R 15 , R ⁇ 7 and R 18 are hydrogen and R 14 and R 22 together form a C 2 -C 3 alkylene chain; and when b) Q is Q 1 , R 14 and R 22 do not together form a C 2 -C 3 alkylene chain, A- t is C(R ⁇ 4 R 15 ), or A is NR 16 and A 2 is oxygen; and when c) Q is Q 3 , exhibit herbicidal action.
  • the compounds of formula I can also be prepared by methods known perse described, for example, in WO 97/46530 or WO 00/15615 or WO 00/39094.
  • p is 0 or 1 ;
  • R is a d-C 6 alkylene, C 3 -C 6 alkenylene or C 3 -C 6 alkynylene chain, which may be substituted one or more times by halogen or by R 5 , the unsaturated bonds of the chain not being attached directly to the substituent X ⁇
  • X is oxygen, -O(CO)-, -(CO)O-, -O(CO)O-, -N(R 6 )-O-, -O-NR 5 r, thio, sulfinyl, sulfonyl, -SO 2 NR 7 -, -NR 52 SO 2 - or -NR 8 -;
  • R 2 is a C C 8 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl group, which is substituted one or more times by halogen, hydroxy, amino, formyl, nitro, cyano, mercapto, carbamoyl, d-C 6 alkoxy, d-C 6 alkoxycarbonyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, C 3 -C 6 - cycloalkyl, halo-substituted C 3 -C 6 cycloalkyl, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, CrCehaloalkoxy, C 3 -C 6 haloalkenyloxy, cyano-CrC 6 alkoxy, d-Cealk
  • R 3 is C ⁇ -C 3 haloalkyl
  • R 4 is hydrogen, halogen, C C 3 alkyl, d-C 3 haloalkyl, C C 3 alkoxy, CrC 3 alkoxy-CrC 3 alkyl or
  • R 5 is hydroxy, CrC 6 alkoxy, C 3 -C 8 cycloalkyloxy, CrCealkoxy-CrC 6 alkoxy, d-C 6 alkoxy- CrC 6 alkoxy-CrCealkoxy or CrC 2 alkylsulfonyloxy;
  • R 6 , R 7 , R 8 , R 9 , R 10 , Ru, R- ⁇ 2 , R5 1 and R 52 are each independently of the others hydrogen, d-C 6 alkyl, d-C 6 haloalkyl, CrC 8 alkoxycarbonyl, CrC 6 alkylcarbonyl, CrC 6 alkoxy-CrC 6 alkyl, CrC 6 alkoxy-CrCealkyl substituted by CrC 6 alkoxy, benzyl, or phenyl, wherein phenyl and benzyl may in turn be substituted one or more times by d-C 6 alkyI, CrCehaloalkyl, CrCealkoxy, d-C 6 haloalkoxy, halogen, cyano, hydroxy or by nitro; wherein R 6 is not hydrogen when R 9 is hydrogen, d-C 6 alkoxycarbonyl or d-C 6 alkylcarbonyl; Q is Qi
  • Ai is C(R 14 R 15 ), NR 16 or oxygen
  • R ⁇ 7 and R 18 being each independently of the other d-C 4 alkoxy, C C 4 - alkylthio, d-C 4 alkylsulfinyl or CrC 4 alkylsulfonyl; and that Ai is other than NR 16 when A 2 is thio, sulfinyl or C(R 17 R 18 ), R 17 and R 18 being each independently of the other d-C alkoxy, d-C 4 alkyIthio, CrC 4 alkylsulfinyl or CrC 4 alkylsulfonyl;
  • R 14 and R 22 are each independently of the other hydrogen, C C 4 alkyl, d-C 4 haloalkyl, C 3 -C 4 - alkenyl, C 3 -C 4 alkynyl, d-C 4 alkylthio, d-C 4 alkylsulfinyl, d-C 4 alkylsulfonyl, C C 4 alkylsulfonyI- oxy, CrC 4 alkoxy, C C alkoxycarbonyl or d-C 4 alkylcarbonyl;
  • R 15 and R 21 are each independently of the other hydrogen, d-C 4 alkyl, CrC 4 haloalkyl, C 3 -C - alkenyl or C 3 -C 4 alkynyl;
  • R 17 is hydrogen, C C 4 alkyl, d-C 4 haloalkyl, d-C alkoxy, d-C 4 alkylthio, C C 4 alkylsulfinyl or
  • R 18 is hydrogen, d-C 4 alkyl, d-C haloalkyl, C 3 -C 4 alkenyl, C 3 -C alkynyl, C C 4 alkoxy, C C 4 - alkylthio, C C 4 alkylsulfinyl, d-C alkylsulfonyl or di(CrC )alkoxyalkyI-CrC alkyl;
  • R 20 is d-C alkyl, C 3 -C 6 cycloalkyl, C 3 -C 4 alkenyl, C 3 -C 4 alkynyl, d-C 4 alkylcarbonyl, d-C 4 alkyl- carbonyloxy, di(C ⁇ -C )alkylaminocarbonyl or benzyl, wherein the phenyl group may be substituted one or more times by CrC 6 alkyl, d-C 6 haloalkyl, d-C 6 alkoxy
  • R 19 and R 16 are each independently of the other hydrogen, d-C 4 alkyl, C 3 -C 6 cycloalkyl,
  • C 2 -C alkylene chain which may be interrupted by oxygen and/or by carbonyl and/or by sulfur, with the proviso that the oxygen and sulfur atoms are separated by at least one methylene group; or R 14 and R 18 together form a C 2 -C alkylene chain; or
  • R 22 and R 18 together form a C 2 -C 4 alkylene chain; or R 18 forms, together with R 22 or Ru, a direct bond; or R 16 and R 18 together form a C 2 -C 4 alkylene chain;
  • R 13 is hydroxy; O " M + wherein M + is an alkali metal cation or an ammonium cation; halogen, d-C 12 alkylsulfonyloxy, amino, d-C 4 alkylthio, d-C 2 alkylsulfinyl, C C ⁇ 2 alkylsulfonyl, C C ⁇ 2 - haloalkylthio, C C 12 haloalkylsulfinyl, d-C ⁇ 2 haloalkylsulfonyl, CrC 6 alkoxy-CrC 6 alkylthio,
  • R 13 is phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, phenylsulfonylamino, phenyl- sulfonyloxy or benzoyloxy, wherein the phenyl groups may in turn be substituted by one or more halogen, nitro, cyano, C C alkyI, d-C 4 haloalkyl, C C alkoxy or d-C haloalkoxy groups; or R 13 is a group Hetrthio, Het 2 -sulfinyl, Het 3 -sulfonyf, Het 4 -(CO)O or Het 5 -N(R 33 ); wherein Het,, Het 2 , Het 3 , Het 4 and
  • R23, R2 , R25, R26, R27, 28, R29, R30 and R 33 are each independently of the others hydrogen or
  • R 23 and R 24 together or R 25 and R 26 together or R 27 and R 28 together or R 29 and R 30 together are pyrrolidino, piperidino, morpholino or thiomorpholino, each of which may be mono- or poly-substituted by methyl groups; or Q is Q 2
  • R ⁇ is hydrogen, d-C 4 alkyl, d-C 4 haloalkyl, C 3 -C 6 cycloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl or benzyl, wherein the phenyl group may be substituted one or more times by CrC 6 alkyl,
  • R 35 is hydrogen, d-C 4 alkyl, d-C 4 haloalkyl, C 3 -C 6 cycloalkyI, C 3 -C 4 alkenyl, C 3 -C 4 alkynyl or benzyl, wherein the phenyl group may be substituted one or more times by CrC 6 alkyl,
  • R 36 is hydroxy; O " M + wherein M + is an alkali metal cation or an ammonium cation; halogen,
  • R 37 and R 38 together or R 39 and R 40 together or R 41 and R 42 together or R 43 and R ⁇ together are pyrrolidino, piperidino, morpholino or thiomorpholino, each of which may be mono- or poly-substituted by methyl groups; or Q is Q 3
  • R 9 is C ⁇ -C 4 alkyl, C ⁇ -C 4 haloalkyl, C 3 -C 6 cycloalkyl or halo-substituted C 3 -C 6 cycloalkyl;
  • R 5 o is d-C 3 alkylene, which may be substituted by halogen, hydroxy, CrC 6 alkoxy, C 2 -C 6 - alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, d-Cealkoxy-CrCealkoxy, CrC 6 alkoxy-CrC 6 alkoxy- d-C 6 alkoxy, (3-oxetanyl)-oxy, or by (3-oxetanyl)-oxy substituted by CrC 6 alkyl, or by benzylthio, benzylsulfinyl, benzylsulfonyl, phenyl, phenoxy, phenylthi
  • -R XrR 2 is other than d-C 4 alkoxy-CrC 4 alkoxy-CrC 4 alkyl when a) Q is Q 1 wherein A 1 is C(R 14 R 15 ) and A 2 is C(R 17 R 18 ), R 15 , R 17 and R 18 are hydrogen and R 14 and R 22 together form a C 2 -C 3 alkylene chain; and when b) Q is Q L R and R 22 do not together form a C 2 -C 3 alkylene chain, A- is C(R 14 R 15 ), or A-i is NR 16 and A 2 is oxygen; and when c) Q is Q 3 , and b) a synergistically effective amount of one or more compounds selected from a compound of formula 2.1
  • R 51 is CH 2 -OMe, ethyl or hydrogen
  • R 56 is CH(Me)-CH 2 OMe or ⁇ S>CH(Me)-CH 2 OMe; and a compound of formula 2.4
  • R 57 is chlorine, methoxy or methylthio
  • R 58 is ethyl or isopropyl
  • R 59 is ethyl, isopropyl, -C(CN)(CH 3 )-CH 3 or tert-butyl; and a compound of formula 2.5
  • R 60 is ethyl or n-propyl
  • R 61 is COO " 1/2 Ca ⁇ , -CH 2 -CH(Me)S-CH 2 CH 3) the group
  • the group T I and X is oxygen, N-O-CH 2 CH 3 or
  • R 62 is hydrogen, methoxy or ethoxy
  • R 63 is hydrogen, methyl, methoxy or fluorine
  • R 64 is COOMe, fluorine or chlorine
  • R 65 is hydrogen or methyl
  • Y is methine, C-F or nitrogen
  • Z is methine or nitrogen
  • R 66 is fluorine or chlorine
  • R 67 is hydrogen or -C(O)-S-n-octyl; and a compound of formula 2.8
  • R 68 is either bromine or iodine; and a compound of formula 2.9
  • R 6 g is chlorine or nitro; and a compound of formula 2.10
  • R 70 is fluorine or chlorine, and R 71 is -CH 2 -CH(CI)-COOCH 2 CH 3 or -NH-SO 2 Me; and a compound of formula 2.1 1
  • R 72 is trifluoromethyl or chlorine; and a compound of formula 2.12
  • R 73 is NH 2 or ⁇ S>NH 2 ; and a compound of formula 2.13 wherein Y 2 is nitrogen, methine, C-NH-CHO, C-CH 2 -NH-SO 2 CH 3 or N-Me, V ⁇ is nitrogen, methine, C-CI or C-l, Y 3 is methine, Y 4 is methine or Y 3 and Y 4 together are sulfur or C-CI, Y 5 is nitrogen or methine, Y 6 is methyl, difluoromethoxy, trifluoromethyl or methoxy, Y 7 is methoxy or difluoromethoxy and R 74 is CONMe 2 , COOMe, COOC 2 H 5 , trifluoromethyl, CH 2 -CH 2 CF 3 , O-CH 2 -CH 2 CI or SO 2 CH 2 CH 3 , or a sodium salt thereof ("Me" being in each case the methyl group); and the compound of formula 2.13.c
  • Ro ⁇ > R 02 and R 03 are each independently of the others halogen, nitro, cyano, d-C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, CrC 4 haloalkyl, C 2 -C 6 haloalkenyl, C 3 -C 6 cycloalkyl, halo- substituted C 3 -C 6 cycloalkyl, CrC 6 alkoxyalkyl, CrC 6 alkylthioalkyl, hydroxy, mercapto, d-C 6 alkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyIoxy, d-C alkylcarbonyl, d-C 4 alkoxycarbonyl, C C 4 alkylthio, CrC alkylsulfinyl, d-C 4 alkylsulfonyl, amino, C r C 4 alkylamino or di(d- C
  • R027, R028 and R029 are, each independently of the others, hydrogen, halogen, d-C 4 alkyl or d-C 4 haloalkyl, it being possible for an alkylene ring, which together with the carbon atoms of the group 7.
  • Z 2 or Z 3 contains from 2 to 6 carbon atoms and which may be interrupted by oxygen, to be either fused or spiro-bound to the carbon atoms of the group Z 1 ; Z 2 or Z 3 or that alkylene ring bridges at least one ring atom of the group Z ⁇ Z ⁇ or Z 3 ;
  • G is hydrogen, -CfX -R ⁇ o, -C(X 2 )-X 3 -R 0 3i , -C(X 4 )-N(R 03 2)-Ro33, -SO 2 -R 034 , an alkali metal cation, alkaline earth metal cation, sulfonium cation or ammonium cation or -P(X 5 )(Ro35)-Ro 36 ; i, X 2 , 3 , X 4 and X 5 are each independently of the others oxygen or sulfur; and Roso, R03 1 , Ro32, R033, R 0 3 4 , Ross and
  • prosulfocarb picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P- ethyl, diclof op-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlorotoluron, isoproturon, metazazthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, trifluralin, fluthiamide, isoxaben, triallate, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac
  • the invention also includes the salts that the compounds of formula I are able to form with amines, alkali metal and alkaline earth metal bases or quaternary ammonium bases.
  • alkali metal and alkaline earth metal hydroxides used as salt formers emphasis is to be given to the hydroxides of lithium, sodium, potassium, magnesium and calcium, but especially to those of sodium and potassium.
  • Suitable amines for ammonium salt formation are ammonia as well as primary, secondary and tertiary d-C 18 alkylamines, d-C 4 hydroxyalkyl- amines and C 2 -C alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four butylamine isomers, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methyl-ethylamine, methyl-isopropylamine, methyl- hexylamine, methyl-nonylamine, methyl-pentadecylamine, methyl-octa
  • R 2 is -CH 2 OCH 3 , -CH 2 OCH 2 CH 3 , -CH 2 CH 2 OCH 3 , -CH 2 CH 2 SO 2 CH 3 or -CH 2 CH 2 OCH 2 CH 2 OCH 3 , preferably -CH 2 CH 2 OCH 3 , with prominence being given to those compounds wherein X ⁇ is oxygen and Ri is -CH 2 -.
  • preference is given to those wherein Q is Qi and R 13 is hydroxy.
  • R 2 for example in the case of , the attachment position is located at the carbon atom identified by "CH".
  • R 3 is CF 3 , CF 2 CF 3 , CF 2 CI, CF 2 H or CCI 3 , especially CF 3 , R 4 preferably being hydrogen or methyl, especially hydrogen.
  • R 6 , R 7 , Rs, Rg, R10, R1 1 , R12, R51 and R 52 are each independently of the others especially hydrogen, d-C 4 alkyl, CrC 6 alkoxy-CrCealkyl, or CrC 6 alkoxy-CrC 6 alkyl substituted by d-C 6 alkoxy, while in addition, in a preferred group of compounds of formula I, Q is Q 2 and Ri is methylene.
  • Q being Q ⁇ and R 13 being hydroxy or halogen, especially hydroxy.
  • A- is C(R 14 R ⁇ 5 ) or NR 16
  • a 2 is C(R 17 R ⁇ 8 ), C(O) or oxygen
  • A-i is C(R 14 R 15 ) and A 2 is C(R ⁇ 7 R 18 ), and R 14 and R 22 together form a C 2 -C 3 alkylene chain, preferably an ethylene chain, R 1 5, R ⁇ 7 , R 1 8 and R 2 ⁇ being especially hydrogen; or
  • a 2 is C(O) or C(R 17 R 18 ),
  • A- is C(R 14 R 15 ), and R 14 , R 15 , R 17 and R 18 are each independently of the others hydrogen, methyl, ethyl, methoxycarbonyl or ethoxycarbonyl; or d) R 14 and R 15 together or R 21 and R 22 together form
  • Q is Q 3
  • R 49 is cyclopropyl
  • R 50 -S(O) n is methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl.
  • Preferred synergistic mixtures according to the invention comprise as active ingredients a compound of formula I and either the compound of formula 2.2.a Q
  • R 53 is ethyl, R 54 is ethyl and R 55 is methoxymethyl, or a compound of formula 2.3, or a compound of formula 2.30, or a compound of formula 2.4, or a compound of formula 2.13, or the compound of formula 2.14, or the compound of formula 2.6
  • R 62 is hydrogen, Z is methine, R 63 is methyl, Y is nitrogen, R 64 is fluorine, R 65 is hydrogen and R 66 is fluorine or wherein R 62 is methoxy, Z is methine, R 63 is methoxy, Y is methine, R 6 is chlorine, R 6 s is methyl and R 66 is chlorine, or the compound of formula 2.7 wherein R 67 is -C(O)-S-n-octyl, or a compound of formula 2.12, or the compound of formula 2.18, or the compound of formula 2.19, or the compound of formula 2.21 , or the compound of formula 2.25, or the compound of formula 2.33,
  • Especially preferred synergistic mixtures according to the invention comprise as active ingredients a compound of formula I and either the compound of formula 2.2.a
  • synergistic mixtures comprise as active ingredients a compound of formula I and a compound of formula 2.52a as indicated in Table 1 :
  • chloroacetyl-2-ethyl-6-methylaniline have been found to be very especially effective compositions.
  • CH case of the attachment position is located at the carbon atom identified by "CH".
  • A421 CH CHCH 2 ° ⁇ CH 2 H CF 3 O 0
  • A422 CH CHCH 2 ⁇ ⁇ CH 2 H CF 3 O 0
  • A423 CH CHCH 2 CH, H CF 3 O 0
  • Q is Qi, and Qi is the radical B39:

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Abstract

Herbicidal composition that, in addition to comprising customary inert formulation adjuvants, comprises a) a compound of formula (I), wherein the substituents are as defined in claim 1, or an agronomically acceptable salt of that compound, and b) a synergistically effective amount of one or more compounds of formulae 2.1 to 2.53 and the compounds prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlorotoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, trifluralin, fluthiamide, isoxaben, triallate, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin. The compositions according to the invention may also comprise a safener.

Description

Herbicidal composition
The present invention relates to a novel herbicidal composition comprising a herbicidal active ingredient combination that is suitable for the selective control of weeds in crops of useful plants, for example in crops of maize. The invention relates also to a method of controlling weeds in crops of useful plants and to the use of the novel composition for that purpose.
The compounds of formula I
wherein p is 0 or 1 ;
R is a d-dalkylene, C3-C6alkenylene or C3-C6alkynylene chain, which may be substituted one or more times by halogen or by R5, the unsaturated bonds of the chain not being attached directly to the substituent X^
X! is oxygen, -O(CO)-, -(CO)O-, -O(CO)O-, -N(R6)-O-, -O-NR51-, thio, sulfinyl, sulfonyl,
-SO2NR7-, -NR52SO2- or -NR8-;
R2 is a Cι-C8alkyl, C3-C6alkenyl or C3-C6alkynyl group, which is substituted one or more times by halogen, hydroxy, amino, formyl, nitro, cyano, mercapto, carbamoyl, C C6alkoxy,
CrC6alkoxycarbonyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, C3-C6- cycloalkyl, halo-substituted C3-C6cycloalkyl, C3-C6alkenyloxy, C3-C6alkynyloxy, C C6halo- alkoxy, C3-C6haloalkenyloxy, cyano-d-C6alkoxy, d-C6alkoxy-Cι-C6alkoxy, d-C6alkoxy- d-Cealkoxy-CrCealkoxy, d-Cealkylthio-CrCealkoxy, Cι-C6alkylsulfinyl-d-C6alkoxy, d-C6- alkylsulfonyl-C C6alkoxy, d-C6alkoxycarbonyl-Cι-C6alkoxy, C C6alkoxycarbonyl, C C6- alkylcarbonyl, d-C6alkylthio, d-Cealkylsulfinyl, d-C6alkylsulfonyl, d-C-ehaloalkylthio,
CrC6haloalkylsulfinyl, CrC6haloalkylsulfonyl, oxiranyl (which may in turn be substituted by d-C6alkyl), (3-oxetanyl)-oxy (which may in turn be substituted by d-C6alkyl), benzylthio, benzylsulfinyl, benzylsulfonyl, d-C6alkylamino, di(C C6alkyl)amino, R9S(O)2O,
RιoN(Rn)SO2-, rhodano, phenyl, phenoxy, phenylthio, phenylsulfinyl or by phenylsulfonyl; wherein the phenyl- or benzyl-containing groups may in turn be substituted by one or more d-dalkyl, d-C-6haloalkyl, d-C6alkoxy, Cι-C6haloalkoxy, halogen, cyano, hydroxy or nitro groups, or
R2 is phenyl, which may be substituted one or more times by d-C6alkyl, CrC6haloalkyl, d-C6alkoxy, d-C6haloalkoxy, halogen, cyano, hydroxy or by nitro; or R2 is C3-C6cycloalkyl; C3-C6cycloalkyl substituted by C C6alkoxy or by d-C6alkyl; 3-oxetanyl or 3-oxetanyl substituted by d-C6alkyl; or, when Q is Q2 or Q3, or when Q is Q^ wherein R14 and R22 denote a C2-C3alkylene chain, R2 may additionally be a five- to ten-membered, monocyclic or fused bicyclic ring system, which may be aromatic, saturated or partially saturated and which may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur, the ring system being bonded to the substituent X^ directly or via a C C4alkylene, C2-C4alkenyl-d-C4alkylene, C2-C4alkynyl- d-C4alkylene, -N(R12)-C C4alkylene, -SO-d-C4alkylene or -SO2-C C4alkylene group, and wherein each ring system may contain no more than two oxygen atoms and no more than two sulfur atoms and the ring system may itself be mono-, di- or tri-substituted by d-C6alkyl, d-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, d-C6alkoxy, hydroxy, d-C6haloalkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, mercapto, CrC6alkylthio, d-Cehaloalkylthio, C3-C6alkenylthio, C3-C6haloalkenylthio, C3-C6alkynyIthio, C2-C5alkoxyalkylthio, C3-C5acetylalkylthio, C3-C6alkoxycarbonylalkylthio, C2-C4cyanoalkylthio, C C6alkylsulfinyl, d-C6haloalkylsulfinyl, d-C6alkylsulfonyl, d-C6haloalkylsulfonyl, aminosulfonyl, d-C2alkylaminosulfonyl, di(d-C2alkyl)aminosulfonyl, di(C C4alkyl)amino, halogen, cyano, nitro, phenyl or by benzylthio, wherein phenyl and benzylthio may in turn be substituted on the phenyl ring by d-C3alkyl, d-C3haloalkyl, C C3alkoxy, d-C3haloalkoxy, halogen, cyano or by nitro, and wherein the substituents on the nitrogen in the heterocyclic ring are other than halogen; or R2 is hydrogen or unsubstituted d-C8alkyl, when either a) R! is substituted by the group R5, or b) Q is the group Q2, or c) Q is the group Q3 wherein X1 is -O(CO)-, -(CO)O-, -N(R6)-O-, -O-NR51-, -SO2NR7-, -NR52SO2- or -NR8-; or d) Q is the group Q^ wherein X is -N(R6)-O-, -O-NR51-, -SO2NR7-, -NR52SO2- or -NR8-, or e) Q is the group Qi wherein R14 and R22 in Qi denote a C2-C3alkylene chain and X! is -O(CO)- or -(CO)O-;
R3 is C C3haloalkyl; R4 is hydrogen, halogen, d-C3alkyl, CrC3haloalkyl, C C3alkoxy, d-Csalkoxy-d-Csalkyl or d-C3alkoxy-CrC3alkoxy;
R5 is hydroxy, d-C6alkoxy, C3-C6cycloalkyloxy, d-Cealkoxy-d-Cβalkoxy, d-C6alkoxy-
C Cβalkoxy-C Cealkoxy or CrC2alkylsulfonyloxy;
R6, R7, R8, Rg, R10, R11, R12, R51 and R52 are each independently of the others hydrogen, d-C6alkyl, C C6haloalkyl, d-C6alkoxycarbonyl, CrC6alkylcarbonyl, C Cβalkoxy-d-Cealkyl, d-Cealkoxy-d-Cεalkyl substituted by CrC6alkoxy, benzyl, or phenyl, wherein phenyl and benzyl may in turn be substituted one or more times by d-C6alkyl, d-C6haloalkyl, d-C6- alkoxy, d-C-6haloalkoxy, halogen, cyano, hydroxy or by nitro; wherein R6 is not hydrogen when R9 is hydrogen, d-C6alkoxycarbonyl or d-C6alkylcarbonyl;
Q is Q!
wherein
A! is C(R14R15), NR16 or oxygen;
A2 is C(R17R18), C(O), -C=N-O-R19, oxygen, thio, sulfinyl, sulfonyl, -NR20 or ethylene; with the provisos that is other than oxygen when A2 is oxygen, C(O), thio, sulfinyl, -C=N-O-R19)
NR20 or C(R17R18), R17 and Rι8 being each independently of the other C C4alkoxy, C C - alkylthio, CrC4aIkylsulfinyl or Cι-C alkylsulfonyl; and that A1 is other than NR16 when A2 is thio, sulfinyl or C(R17R18), R17 and R18 being each independently of the other C C4alkoxy, d-C4alkylthio, Cι-C alkylsulfinyl or C C4alkylsulfonyl;
Ru and R22 are each independently of the other hydrogen, Cι-C alkyl, C C4haloalkyl, C3-C4- alkenyl, C3-C4alkynyl, d-C4alkylthio, d-C4alkylsulfinyl, d-C4alkylsulfonyl, d-C4aIkylsulfonyl- oxy, d-C alkoxy, Cι-C4alkoxycarbonyl or d-C4alkylcarbonyl;
R15 and R21 are each independently of the other hydrogen, d-C4alkyl, d-C4haloalkyl, C3-C4- alkenyl or C3-C4alkynyl;
R17 is hydrogen, C^C^Ikyl, C C4haloalkyl, Cι-C4alkoxy, C C4alkylthio, d-C4alkylsulfinyl or
Cι-C4alkylsulfonyl; R18 is hydrogen, d-C4alkyl, Cι-C4haIoalkyl, C3-C4alkenyl, C3-C4alkynyl, d-C4alkoxy, C C4- alkylthio, C C4alkylsulfinyl, d-C4alkylsulfonyl or di(d-C4)alkoxyalkyl-d-C4alkyl;
R20 is d-C4alkyl, C3-C6cycloalkyl, C3-C4alkenyl, C3-C4alkynyl, d-C4alkylcarbonyl, C C4alkyl- carbonyloxy, di(Cι-C4)alkylaminocarbonyl or benzyl, wherein the phenyl group may be substituted one or more times by CrCealkyl, d-C-6haloalkyl, CrC6alkoxy, CrC6haloalkoxy, halogen, cyano, hydroxy or by nitro;
R19 and R16 are each independently of the other hydrogen, d-C4alkyl, C3-C6cycloalkyl,
C3-C4alkenyl, C3-C4alkynyl, benzyl or phenyl, wherein phenyl and benzyl may in turn be substituted one or more times by d-C6alkyl, CrC6haloalkyl, d-C6alkoxy, CrC6haloalkoxy, halogen, cyano, hydroxy or by nitro; or R14 and R22 together form a C2-C3alkylene chain; or Rι4 and R15 together and/or R17 and R18 together and/or R21 and R22 together form a
C2-C alkylene chain, which may be interrupted by oxygen and/or by carbonyl and/or by sulfur, with the proviso that the oxygen and sulfur atoms are separated by at least one methylene group; or Ri4 and R 8 together form a C2-C4alkylene chain; or
R22 and R18 together form a C2-C alkylene chain; or R18 forms, together with R22 or R14, a direct bond; or R 6 and R18 together form a C2-C4alkylene chain;
R13 is hydroxy; O"M+ wherein M+ is an alkali metal cation or an ammonium cation; halogen, d-Cι2alkylsulfonyloxy, amino, d-C4alkylthio, d-C12alkylsulfinyl, CrC12alkylsulfonyl, d-C12- haloalkylthio, C C12haloalkylsulfinyl, d-Cι2haloalkylsulfonyl, CrC6alkoxy-CrC6alkylthio,
CrC6alkoxy-CrC6alkylsulfinyl, CrC6alkoxy-CrC6alkylsulfonyl, C3-Cι2alkenylthio, C3-C12- alkenylsulfinyl, C3-Cι2alkenylsulfonyl, C3-Cι2alkynylthio, C3-Cι2alkynylsulfinyl, C3-C12alkynyl- sulfonyl, C C4alkoxycarbonyl-CrC4alkylthio, d-C4alkoxycarbonyl-CrC alkylsulfinyl, d-C4- alkoxycarbonyl-d-C4alkylsulfonyl, (d-C4alkoxy)2P(O)O, C C4alkyl-(CrC4alkoxy)P(O)O,
H(C C4alkoxy)P(O)O, R23R24N, R25R26NNH, R27R28NC(O)O-, R29R30NC(O)NH-, C C18alkyl- carbonyloxy, C2-C18alkenylcarbonyloxy, C2-Cι8alkynylcarbonyloxy, C3-C6cycloalkylcarbonyl- oxy, d-C12alkoxycarbonyloxy, CrC12alkylthiocarbonyloxy or d-Cι2alkylthiocarbamoyl, wherein the alkyl, alkenyl and alkynyl groups may be substituted by halogen, d-C6alkoxy,
CrC6alkylthio, C C6alkylsulfinyl, d-C6alkylsulfonyl or by cyano; or R-I3 is phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, phenylsulfonylamino, phenyl- sulfonyloxy or benzoyloxy, wherein the phenyl groups may in turn be substituted by one or more halogen, nitro, cyano, d-C4alkyl, C C4haloalkyl, CrC4alkoxy or d-C4haloalkoxy groups; or R13 is a group Hetrthio, Het2-sulfinyl, Het3-sulfonyl, Het4-(CO)O or Het5-N(R33); wherein
Het1 ; Het2, Het3, Het4 and Het5 are each independently of the others a five- to ten- membered, monocyclic or fused bicyclic ring system, which may be aromatic or partially saturated and which may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur and wherein each ring system may contain no more than two oxygen atoms and no more than two sulfur atoms and the ring system may itself be substituted by d-C6alkyl, d-Cehaloalkyl, d-C6alkoxy, C C6haloalkoxy, C C6alkylthio, CrC6alkylsulfinyl, d-
C6alkylsulfonyl, di(d-C alkyl)aminosulfonyl, di(CrC4alkyl)amino, halogen, cyano, nitro or by phenyl, and wherein the substituents on the nitrogen in the heterocyclic ring are other than halogen;
R23, R2 , R25, R26, R27, R28, R29, R30 and R33 are each independently of the others hydrogen or
C C6alkyl; or R23 and R24 together or R25 and R26 together or R27 and R28 together or R29 and R30 together are pyrrolidino, piperidino, morpholino or thiomorpholino, each of which may be mono- or poly-substituted by methyl groups; or Q is Q2
wherein
R34 is hydrogen, d-C4alkyl, d-C4haloalkyl, C3-C6cycloalkyl, C2-C4alkenyl, C2-C4alkynyl or benzyl, wherein the phenyl group may be substituted one or more times by d-C6alkyl, d-C6haloalkyl, d-C6alkoxy, CrCehaloalkoxy, halogen, cyano, hydroxy or by nitro;
R35 is hydrogen, d-dalkyl, d-dhaloalkyl, C3-C6cycloalkyl, C3-C4alkenyl, C3-C4alkynyl or benzyl; wherein the phenyl group may be substituted one or more times by d-C6alkyl, d-C-ehaloalkyl, CrC6alkoxy, C C6haloalkoxy, halogen, cyano, hydroxy or by nitro;
R36 is hydroxy; O"M+ wherein M+ is an alkali metal cation or an ammonium cation; halogen, d-C12alkylsulfonyloxy, amino, d-dalkylthio, CrC12alkylsulfinyl, d-d2alkylsulfonyl,
CrC12haloalkylthio, d-C12haloalkylsulfinyl, C C12haloalkylsulfonyl, Cι-C6alkoxy-CrC6alkyl- thio, d-Cealkoxy-d-Cealkylsulfinyl, d-C6alkoxy-CrC6alkylsulfonyl, C3-C12alkenylthio, C3-C12alkenylsulfinyl, C3-C 2alkenylsulfonyl, C3-Cι2alkynylthio, C3-C12alkynylsulfinyl, C3-C12alkynylsulfonyl, d-dalkoxycarbonyl-CrC4alkylthio, C C4alkoxycarbonyl-CrC4alkyl- sulfinyl, C C4alkoxycarbonyl-CrC4alkylsulfonyl, (d-C4alkoxy)2P(O)O, d-C4alkyl- (d-C4alkoxy)P(O)O, H(CrC4alkoxy)P(O)O, R37R38N, R39R40NNH, R41R42NC(O)O-, R R4 NC(O)NH-, d-C18alkylcarbonyloxy, C2-C18alkenylcarbonyloxy, C2-C18alkynylcarbonyl- oxy, C3-C6cycloalkylcarbonyloxy, C C12alkoxycarbonyloxy, CrC12alkylthiocarbonyloxy or CrC 2alkylthiocarbamoyl, wherein the alkyl, alkenyl and alkynyl groups may be substituted by halogen, d-C6alkoxy, CrC6alkylthio, CrC6alkylsulfinyl, d-C6alkylsulfonyl or by cyano; or R36 is phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, phenylsulfonylamino, phenyl- sulfonyloxy or benzoyloxy, wherein the phenyl groups may in turn be substituted one or more times by halogen, nitro, cyano, d-C4alkyl, C C4haloalkyl, C C4alkoxy or by C C4halo- alkoxy, or R36 is a group Het7-thio, Het8-sulfinyl, Het9-sulfonyl, Het10-(CO)O or Het1rN(R47); wherein Het7, Het8, Het9, Het10 and Het^ are each independently of the others a five- to ten- membered, monocyclic or fused bicyclic ring system, which may be aromatic or partially saturated and which may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur and wherein each ring system may contain no more than two oxygen atoms and no more than two sulfur atoms and the ring system may itself be substituted by d-C6alkyl, d-Cehaloalkyl, CrC6alkoxy, C C6haloalkoxy, d-C6alkylthio, d-C6alkylsulfinyl, CrCealkylsulfonyl, di(d-C4alkyl)aminosulfonyl, di(Cι-C alkyl)amino, halogen, cyano, nitro or by phenyl, and wherein the substituents on the nitrogen in the heterocyclic ring are other than halogen; R37, R38, 39> R4o, R41, R42> R-w. R44 and R 7 are each independently of the others hydrogen or CrC6alkyl; or
R37 and R38 together or R39 and R40 together or R41 and R42 together or R43 and R^ together are pyrrolidino, piperidino, morpholino or thiomorpholino, each of which may be mono- or poly-substituted by methyl groups; or Q is Q3
wherein R49 is d-C4alkyl, d-C4haloalkyl, C3-C6cycloalkyl or halo-substituted C3-C6cycloalkyl;
R50 is CrC3alkylene, which may be substituted by halogen, hydroxy, d-C6alkoxy, C2-C6- alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, d-C-ealkoxy-d-Cealkoxy, CrC6alkoxy-CrC6alkoxy- d-C6alkoxy, (3-oxetanyl)-oxy, or by (3-oxetanyl)-oxy substituted by CrC6alkyl, or by benzylthio, benzylsulfinyl, benzylsulfonyl, phenyl, phenoxy, phenylthio, phenylsulfinyl or by phenylsulfonyl, wherein the phenyl- and benzyl-containing groups may in turn be substituted by one or more d-C6alkyl, CrC6haloalkyl, d-C6alkoxy, CrCehaloalkoxy, halogen, cyano, hydroxy or nitro groups; or R50 is phenyl, wherein the phenyl-containing group may in turn be substituted by one or more CrC6alkyl, d-C6haloalkyl, CrC6alkoxy, d-C6haloalkoxy, halogen, cyano, hydroxy or nitro substituents, or R50 is C3-C6cycloalkyl, C3-C6cycloalkyl substituted by d-C6alkoxy or by CrC6alkyl, 3- oxetanyl or 3-oxetanyl substituted by CrC6alkyl; and n is 0, 1 or 2; and also agronomically acceptable salts/N-oxides/isomers/enantiomers of such compounds except for the compound 4-hydroxy-3-[2-(2-methoxyethoxyethoxymethyl)-6- trifluoromethylpyridine-3-carbonyl]-bicyclo[3.2.1]oct-3-en-2-one, and with the provisos that
-R Xι-R2 is other than CrC4alkoxy-CrC4aIkoxy-d-C4alkyl when a) Q is QT wherein AT is C(Rι4R15) and A2 is C(R17R18), R15, Rι7 and R18 are hydrogen and R14 and R22 together form a C2-C3alkylene chain; and when b) Q is Q1, R14 and R22 do not together form a C2-C3alkylene chain, A-t is C(Rι4R15), or A is NR16 and A2 is oxygen; and when c) Q is Q3, exhibit herbicidal action.
The compounds of formula I and their preparation are known, for example, from
WO 01/94339. The compounds of formula I can also be prepared by methods known perse described, for example, in WO 97/46530 or WO 00/15615 or WO 00/39094.
Surprisingly, it has now been found that a combination of variable amounts of active ingredients, that is to say a compound of formula I together with one or more of the active ingredients indicated below, which are known and some of which are also commercially available, exhibits a synergistic action that is capable of controlling, both pre-emergence and post-emergence, the majority of weeds occurring especially in crops of useful plants. There is therefore proposed in accordance with the present invention a novel synergistic composition for the selective control of weeds which, in addition to comprising customary inert formulation adjuvants, comprises as active ingredient a mixture of
a) a herbicidally effective amount of a compound of formula I
wherein p is 0 or 1 ;
R is a d-C6alkylene, C3-C6alkenylene or C3-C6alkynylene chain, which may be substituted one or more times by halogen or by R5, the unsaturated bonds of the chain not being attached directly to the substituent X^
X is oxygen, -O(CO)-, -(CO)O-, -O(CO)O-, -N(R6)-O-, -O-NR5r, thio, sulfinyl, sulfonyl, -SO2NR7-, -NR52SO2- or -NR8-;
R2 is a C C8alkyl, C3-C6alkenyl or C3-C6alkynyl group, which is substituted one or more times by halogen, hydroxy, amino, formyl, nitro, cyano, mercapto, carbamoyl, d-C6alkoxy, d-C6alkoxycarbonyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, C3-C6- cycloalkyl, halo-substituted C3-C6cycloalkyl, C3-C6alkenyloxy, C3-C6alkynyloxy, CrCehaloalkoxy, C3-C6haloalkenyloxy, cyano-CrC6alkoxy, d-Cealkoxy-CrCβalkoxy, d-C6alkoxy- CrC6alkoxy-CrC6alkoxy, CrC6alkylthio-CrC6alkoxy, d-Cealkylsulfinyl-d-Cealkoxy, d-C6- alkylsulfonyl-CrC6alkoxy, CrC6alkoxycarbonyl-CrC6alkoxy, CrC6alkoxycarbonyl, d-C6- alkylcarbonyl, Cι-C6alkylthio, CrC6alkylsulfinyl, CrC8alkylsulfonyl, d-C6haloalkylthio, CrC6haloalkylsulfinyl, CrC6haIoalkylsulfonyl, oxiranyl (which may in turn be substituted by CrC6alkyl), (3-oxetanyl)-oxy (which may in turn be substituted by d-C6alkyl), benzylthio, benzylsulfinyl, benzylsulfonyl, d-C6alkylamino, di(CrC6alkyl)amino, R9S(O)2O, R10N(R1ι)SO2-> rhodano, phenyl, phenoxy, phenylthio, phenylsulfinyl or by phenylsulfonyl; wherein the phenyl- or benzyl-containing groups may in turn be substituted by one or more CrC8alkyl, CrC6haloalkyl, CrC6alkoxy, d-C6haloalkoxy, halogen, cyano, hydroxy or nitro groups, or R2 is phenyl, which may be substituted one or more times by d-C6alkyl, CrC6haloalkyl, CrC6alkoxy, CrC6haloalkoxy, halogen, cyano, hydroxy or by nitro; or R2 is C3-C6cycloalkyl; C3-C6cycloalkyl substituted by d-C8alkoxy or by d-C6alkyl; 3-oxetanyl or 3-oxetanyl substituted by d-C6alkyl; or, when Q is Q2 or Q3, or when Q is Qι wherein R14 and R22 denote a C2-C3alkylene chain, R2 is additionally a five- to ten-membered, monocyclic or fused bicyclic ring system, which may be aromatic, saturated or partially saturated and which may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur, the ring system being bonded to the substituent Xi directly or via a d-C alkylene, C2-C4alkenyl-d-C4a!kylene, C2-C4alkynyl- d-C4alkylene, -N(R12)-C C4alkylene, -SO-d-C4alkylene or -SO2-d-C4alkylene group, and wherein each ring system may contain no more than two oxygen atoms and no more than two sulfur atoms and the ring system may itself be mono-, di- or tri-substituted by d-C6alkyl, CrCehaloalkyl, C2-C6alkenyl, C2-C8haloalkenyl, C2-C8alkynyl, C2-C6haloalkynyl, d-C6alkoxy, hydroxy, d-Cehaloalkoxy, C3-C6alkenyIoxy, C3-C6alkynyloxy, mercapto, d-C6alkylthio, CrC6haloalkylthio, C3-C6alkenylthio, C3-C6haloalkenylthio, C3-C6alkynylthio, C2-C5alkoxyalkylthio, C3-C5acetylalkylthio, C3-C6alkoxycarbonylalkylthio, C2-C cyanoalkylthio, CrC6alkylsulfinyl, d-C6haloalkylsulfinyl, CrC6alkylsulfonyl, d-C6haloalkylsulfonyl, aminosulfonyl, d-C2alkylaminosulfonyl, di(d-C2alkyl)aminosulfonyl, di(d-C4alkyl)amino, halogen, cyano, nitro, phenyl or by benzylthio, wherein phenyl and benzylthio may in turn be substituted on the phenyl ring by d-C3alkyl, d-C3haloalkyl, d-C3alkoxy, C C3haloalkoxy, halogen, cyano or by nitro, and wherein the substituents on the nitrogen in the heterocyclic ring are other than halogen; or R2 is hydrogen or unsubstituted d-C8alkyl, when either a) RΪ is substituted by the group R5, or b) Q is the group Q2, or c) Q is the group Q3 wherein X^ is -O(CO)-, -(CO)O-, -N(R6)-O-, -O-NR51-, -SO2NR7-, -NR52SO2- or -NR8-; or d) Q is the group Q wherein X is -N(R6)-O-, -O-NR51-, -SO2NR7-, -NR52SO2- or -NR8-, or e) Q is the group Q-i wherein R14 and R22 in Q^ denote a C2-C3alkylene chain and X^ is -O(CO)- or -(CO)O-;
R3 is Cι-C3haloalkyl;
R4 is hydrogen, halogen, C C3alkyl, d-C3haloalkyl, C C3alkoxy, CrC3alkoxy-CrC3alkyl or
C C3alkoxy-CrC3alkoxy; R5 is hydroxy, CrC6alkoxy, C3-C8cycloalkyloxy, CrCealkoxy-CrC6alkoxy, d-C6alkoxy- CrC6alkoxy-CrCealkoxy or CrC2alkylsulfonyloxy;
R6, R7, R8, R9, R10, Ru, R-ι2, R51 and R52 are each independently of the others hydrogen, d-C6alkyl, d-C6haloalkyl, CrC8alkoxycarbonyl, CrC6alkylcarbonyl, CrC6alkoxy-CrC6alkyl, CrC6alkoxy-CrCealkyl substituted by CrC6alkoxy, benzyl, or phenyl, wherein phenyl and benzyl may in turn be substituted one or more times by d-C6alkyI, CrCehaloalkyl, CrCealkoxy, d-C6haloalkoxy, halogen, cyano, hydroxy or by nitro; wherein R6 is not hydrogen when R9 is hydrogen, d-C6alkoxycarbonyl or d-C6alkylcarbonyl; Q is Qi
wherein
Ai is C(R14R15), NR16 or oxygen;
A2 is C(R17Ri8), C(O), -C=N-O-R19, oxygen, thio, sulfinyl, sulfonyl, -NR20 or ethylene; with the provisos that A^ is other than oxygen when A2 is oxygen, C(O), thio, sulfinyl, -C=N-O-Rι9,
NR20 or C(Rι7R18), Rι7 and R18 being each independently of the other d-C4alkoxy, C C4- alkylthio, d-C4alkylsulfinyl or CrC4alkylsulfonyl; and that Ai is other than NR16 when A2 is thio, sulfinyl or C(R17R18), R17 and R18 being each independently of the other d-C alkoxy, d-C4alkyIthio, CrC4alkylsulfinyl or CrC4alkylsulfonyl;
R14 and R22 are each independently of the other hydrogen, C C4alkyl, d-C4haloalkyl, C3-C4- alkenyl, C3-C4alkynyl, d-C4alkylthio, d-C4alkylsulfinyl, d-C4alkylsulfonyl, C C4alkylsulfonyI- oxy, CrC4alkoxy, C C alkoxycarbonyl or d-C4alkylcarbonyl;
R15 and R21 are each independently of the other hydrogen, d-C4alkyl, CrC4haloalkyl, C3-C - alkenyl or C3-C4alkynyl;
R17 is hydrogen, C C4alkyl, d-C4haloalkyl, d-C alkoxy, d-C4alkylthio, C C4alkylsulfinyl or
C C4alkyIsulfonyl;
R18 is hydrogen, d-C4alkyl, d-C haloalkyl, C3-C4alkenyl, C3-C alkynyl, C C4alkoxy, C C4- alkylthio, C C4alkylsulfinyl, d-C alkylsulfonyl or di(CrC )alkoxyalkyI-CrC alkyl; R20 is d-C alkyl, C3-C6cycloalkyl, C3-C4alkenyl, C3-C4alkynyl, d-C4alkylcarbonyl, d-C4alkyl- carbonyloxy, di(Cι-C )alkylaminocarbonyl or benzyl, wherein the phenyl group may be substituted one or more times by CrC6alkyl, d-C6haloalkyl, d-C6alkoxy, CrC6haloalkoxy, halogen, cyano, hydroxy or by nitro;
R19 and R16 are each independently of the other hydrogen, d-C4alkyl, C3-C6cycloalkyl,
C3-C4alkenyl, C3-C4alkynyl, benzyl or phenyl, wherein phenyl and benzyl may in turn be substituted one or more times by CrC6aIkyl, d-C6haloalkyl, CrC6alkoxy, d-C6haloalkoxy, halogen, cyano, hydroxy or by nitro; or R14 and R22 together form a C2-C3alkylene chain; or R14 and R15 together and/or R17 and R18 together and/or R21 and R22 together form a
C2-C alkylene chain, which may be interrupted by oxygen and/or by carbonyl and/or by sulfur, with the proviso that the oxygen and sulfur atoms are separated by at least one methylene group; or R14 and R18 together form a C2-C alkylene chain; or
R22 and R18 together form a C2-C4alkylene chain; or R18 forms, together with R22 or Ru, a direct bond; or R16 and R18 together form a C2-C4alkylene chain;
R13 is hydroxy; O"M+ wherein M+ is an alkali metal cation or an ammonium cation; halogen, d-C12alkylsulfonyloxy, amino, d-C4alkylthio, d-C 2alkylsulfinyl, C Cι2alkylsulfonyl, C Cι2- haloalkylthio, C C12haloalkylsulfinyl, d-Cι2haloalkylsulfonyl, CrC6alkoxy-CrC6alkylthio,
CrC6alkoxy-CrC6alkylsulfinyl, CrCealkoxy-CrC6alkylsulfonyl, C3-C12alkenylthio, C3-C12- alkenylsulfinyl, C3-C12alkenylsulfonyl, C3-C12alkynylthio, C3-C12alkynylsulfinyl, C3-C12alkynyl- sulfonyl, CrC alkoxycarbonyI-d-C4alkylthio, d-C4alkoxycarbonyl-CrC4alkylsulfinyl, C C4- alkoxycarbonyl-d-C4alkylsulfonyl, (C C4alkoxy)2P(O)O, C C4alkyl-(CrC4alkoxy)P(O)O,
H(d-C4alkoxy)P(O)O, R23R24N, R25R26NNH, R27R28NC(O)O-, R29R30NC(O)NH-, d-Cι8alkyl- carbonyloxy, C2-C18alkenylcarbonyloxy, C2-C18alkynylcarbonyloxy, C3-C6cycloalkylcarbonyl- oxy, d-C12alkoxycarbonyloxy, CrCι2alkylthiocarbonyloxy or CrCι2alkylthiocarbamoyl, wherein the alkyl, alkenyl and alkynyl groups may be substituted by halogen, d-C6alkoxy,
CrC6alkylthio, CrC6alkylsulfinyl, d-C6alkylsulfonyl or by cyano; or R13 is phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, phenylsulfonylamino, phenyl- sulfonyloxy or benzoyloxy, wherein the phenyl groups may in turn be substituted by one or more halogen, nitro, cyano, C C alkyI, d-C4haloalkyl, C C alkoxy or d-C haloalkoxy groups; or R13 is a group Hetrthio, Het2-sulfinyl, Het3-sulfonyf, Het4-(CO)O or Het5-N(R33); wherein Het,, Het2, Het3, Het4 and Het5 are each independently of the others a five- to ten- membered, monocyclic or fused bicyclic ring system, which may be aromatic or partially saturated and which may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur and wherein each ring system may contain no more than two oxygen atoms and no more than two sulfur atoms and the ring system may itself be substituted by d-C6alkyl, d-Cehaloalkyl, CrC6alkoxy, d-C6haloalkoxy, CrC6alkylthio, C C6alkylsulfinyl, C
C6alkylsulfonyl, di(d-C aIkyl)aminosulfonyl, di(C C4alkyl)amino, halogen, cyano, nitro or by phenyl, and wherein the substituents on the nitrogen in the heterocyclic ring are other than halogen;
R23, R2 , R25, R26, R27, 28, R29, R30 and R33 are each independently of the others hydrogen or
Cι-Cβalkyl; or R23 and R24 together or R25 and R26 together or R27 and R28 together or R29 and R30 together are pyrrolidino, piperidino, morpholino or thiomorpholino, each of which may be mono- or poly-substituted by methyl groups; or Q is Q2
wherein
R^ is hydrogen, d-C4alkyl, d-C4haloalkyl, C3-C6cycloalkyl, C2-C4alkenyl, C2-C4alkynyl or benzyl, wherein the phenyl group may be substituted one or more times by CrC6alkyl,
CrCehaloalkyl, d-C6alkoxy, d-C6haloalkoxy, halogen, cyano, hydroxy or by nitro;
R35 is hydrogen, d-C4alkyl, d-C4haloalkyl, C3-C6cycloalkyI, C3-C4alkenyl, C3-C4alkynyl or benzyl, wherein the phenyl group may be substituted one or more times by CrC6alkyl,
CrCehaloalkyl, d-C6alkoxy, CrCehaloalkoxy, halogen, cyano, hydroxy or by nitro;
R36 is hydroxy; O"M+ wherein M+ is an alkali metal cation or an ammonium cation; halogen,
CrC12alkylsulfonyloxy, amino, d-C4alkylthio, d-C12alkylsulfinyl, Crd2alkylsulfonyl,
CrC12haloalkylthio, CrC12haloalkylsulfinyI, d-C12haloalkylsulfonyl, CrC6alkoxy-CrC6alkyl- thio, CrC6alkoxy-CrC6alkylsulfinyl, CrC6alkoxy-CrC6alkylsulfonyl, C3-Cι2alkenylthio,
C3-C12alkenylsulfinyl, C3-Cι2alkenylsulfonyl, C3-C12alkynylthio, C3-C12alkynylsulfinyl,
C3-C12alkynylsulfonyl, CrC4alkoxycarbonyl-Cι-C4alkyithio, CrC4alkoxycarbonyl-d-C4alkyl- sulfinyl, CrC4alkoxycarbonyI-d-C4alkylsulfonyl, (C C4alkoxy)2P(O)O, d-C4alkyl- (d-C4alkoxy)P(O)O, H(d-C4alkoxy)P(O)O, R37R38N, R39R40NNH, R41R42NC(O)O-, R43R NC(O)NH-, CrCι8alkylcarbonyloxy, C2-C18alkenylcarbonyloxy, C2-Cι8alkynylcarbonyl- oxy, C3-C6cycloalkylcarbonyloxy, d-Cι2alkoxycarbonyloxy, d-Cι2alkylthiocarbonyloxy or CrCι2alkylthiocarbamoyl, wherein the alkyl, alkenyl and alkynyl groups may be substituted by halogen, CrC6alkoxy, d-C6alkylthio, CrC6alkylsulfinyl, d-C6alkylsulfonyl or by cyano; or R36 is phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, phenylsulfonylamino, phenyl- sulfonyloxy or benzoyloxy, wherein the phenyl groups may in turn be substituted one or more times by halogen, nitro, cyano, C C alkyl, C C haloalkyl, d-C4alkoxy or by d-C4halo- alkoxy, or R38 is a group Het7-thio, Het8-sulfinyl, Het9-sulfonyl, Het10-(CO)O or Hetι N(R47); wherein Het7, Het8, Het9, Het10 and Het^ are each independently of the others a five- to ten- membered, monocyclic or fused bicyclic ring system, which may be aromatic or partially saturated and which may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur and wherein each ring system may contain no more than two oxygen atoms and no more than two sulfur atoms and the ring system may itself be substituted by CrC6alkyl, CrCehaloalkyl, CrC6alkoxy, C C6haloalkoxy, CrC6alkylthio, C C6alkylsulfinyl, CrCealkylsulfonyl, di(CrC4alkyl)aminosulfonyl, di(CrC alkyl)amino, halogen, cyano, nitro or by phenyl, and wherein the substituents on the nitrogen in the heterocyclic ring are other than halogen; R37, 38, R39, R4o, R41, R42, R43, R^ and R47 are each independently of the others hydrogen or CrC6alkyl; or
R37 and R38 together or R39 and R40 together or R41 and R42 together or R43 and R^ together are pyrrolidino, piperidino, morpholino or thiomorpholino, each of which may be mono- or poly-substituted by methyl groups; or Q is Q3
wherein
R 9 is Cι-C4alkyl, Cι-C4haloalkyl, C3-C6cycloalkyl or halo-substituted C3-C6cycloalkyl; R5o is d-C3alkylene, which may be substituted by halogen, hydroxy, CrC6alkoxy, C2-C6- alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, d-Cealkoxy-CrCealkoxy, CrC6alkoxy-CrC6alkoxy- d-C6alkoxy, (3-oxetanyl)-oxy, or by (3-oxetanyl)-oxy substituted by CrC6alkyl, or by benzylthio, benzylsulfinyl, benzylsulfonyl, phenyl, phenoxy, phenylthio, phenylsulfinyl or by phenylsulfonyl, wherein the phenyl- and benzyl-containing groups may in turn be substituted by one or more d-C6alkyl, CrCehaloalkyl, d-C6alkoxy, d-C6haloalkoxy, halogen, cyano, hydroxy or nitro groups; or R50 is phenyl, wherein the phenyl-containing group may in turn be substituted by one or more CrC6alkyl, d-C6haloalkyl, d-C6alkoxy, d-C6haloalkoxy, halogen, cyano, hydroxy or nitro substituents, or R50 is C3-C6cycloalkyl, C3-C6cycloalkyl substituted by CrC6alkoxy or by d-C6alkyl, 3- oxetanyl or 3-oxetanyl substituted by CrC6alkyI; and n is 0, 1 or 2; or of an agronomically acceptable salt/N-oxide/isomer/enantiomer of such a compound except for the compound 4-hydroxy-3-[2-(2-methoxyethoxyethoxymethyl)-6- trifluoromethylpyridine-3-carbonyl]-bicyclo[3.2.1]oct-3-en-2-one, and with the provisos that
-R XrR2 is other than d-C4alkoxy-CrC4alkoxy-CrC4alkyl when a) Q is Q1 wherein A1 is C(R14R15) and A2 is C(R17R18), R15, R17 and R18 are hydrogen and R14 and R22 together form a C2-C3alkylene chain; and when b) Q is QL R and R22 do not together form a C2-C3alkylene chain, A- is C(R14R15), or A-i is NR16 and A2 is oxygen; and when c) Q is Q3, and b) a synergistically effective amount of one or more compounds selected from a compound of formula 2.1
wherein R51 is CH2-OMe, ethyl or hydrogen;
R52 is hydrogen, or R51 and R52 together are the group -CH=CH-CH=CH-; and a compound of formula 2.2 wherein R53 is ethyl, R54 is methyl or ethyl, and R55 is -CH( e)-CH2OMe, <S>-CH( e)-CH2OMe, CH2OMe or CH2O-CH2CH3; and a compound of formula 2.3
wherein R56 is CH(Me)-CH2OMe or <S>CH(Me)-CH2OMe; and a compound of formula 2.4
wherein R57 is chlorine, methoxy or methylthio, R58 is ethyl or isopropyl, and R59 is ethyl, isopropyl, -C(CN)(CH3)-CH3 or tert-butyl; and a compound of formula 2.5
wherein R60 is ethyl or n-propyl, R61 is COO" 1/2 Ca^, -CH2-CH(Me)S-CH2CH3) the group
the group T I and X is oxygen, N-O-CH2CH3 or
N-O-CH2CH=CH-CI; and a compound of formula 2.6
wherein R62 is hydrogen, methoxy or ethoxy, R63 is hydrogen, methyl, methoxy or fluorine, R64 is COOMe, fluorine or chlorine, R65 is hydrogen or methyl, Y is methine, C-F or nitrogen, Z is methine or nitrogen, and R66 is fluorine or chlorine; and a compound of formula 2.7
wherein R67 is hydrogen or -C(O)-S-n-octyl; and a compound of formula 2.8
wherein R68 is either bromine or iodine; and a compound of formula 2.9
wherein R6g is chlorine or nitro; and a compound of formula 2.10
wherein R70 is fluorine or chlorine, and R71 is -CH2-CH(CI)-COOCH2CH3 or -NH-SO2Me; and a compound of formula 2.1 1
wherein R72 is trifluoromethyl or chlorine; and a compound of formula 2.12
wherein R73 is NH2 or <S>NH2; and a compound of formula 2.13 wherein Y2 is nitrogen, methine, C-NH-CHO, C-CH2-NH-SO2CH3 or N-Me, VΛ is nitrogen, methine, C-CI or C-l, Y3 is methine, Y4 is methine or Y3 and Y4 together are sulfur or C-CI, Y5 is nitrogen or methine, Y6 is methyl, difluoromethoxy, trifluoromethyl or methoxy, Y7 is methoxy or difluoromethoxy and R74 is CONMe2, COOMe, COOC2H5, trifluoromethyl, CH2-CH2CF3, O-CH2-CH2CI or SO2CH2CH3, or a sodium salt thereof ("Me" being in each case the methyl group); and the compound of formula 2.13.c
and the compound of formula 2.14
and the compound of formula 2.15
and the compound of formula 2.16 HOOC N PO(OH)2 (2.16) and ammonium, isopropylammonium, sodium and
H
trimesium salts thereof; and the compound of formula 2.17
and the compound of formula 2.18
and the compound of formula 2.19
and the compound of formula 2.20
and the compound of formula 2.21 and the compound of formula 2.22
and the compound of formula 2.23
and the compound of formula 2.24
and the compound of formula 2.25
and the compound of formula 2.26
and the compound of formula 2.27
and the compound of formula 2.28
CI- Gl¬ and the compound of formula 2.29 and the compound of formula 2.30
and the compound of formula 2.31
and the compound of formula 2.32
and the compound of formula 2.33
and the compound of formula 2.34
and the compound of formula 2.35
and the compound of formula 2.36
and the compound of formula 2.37 (2.37);
and the compound of formula 2.38 (2-38);
CH3
(CH3)2N N O and the compound of formula 2.39 (2.39);
and the compound of formula 2.40 \ / 3 2 (2.40);
CI and the compound of formula 2.41 (2.41);
and the compound of formula 2.42 (2.42);
CH„
I 3
(CH3)3C ° NCONHCHg and the compound of formula 2.43 " N (2.43); and the compound of formula 2.44
and the compound of formula 2.45
and the compound of formula 2.46
and the compound of formula 2.47
and the compound of formula 2.48
and the compound of formula 2.49
and the compound of formula 2.50
and the compound of formula 2.51 and a compound of formula 2.52
wherein
Roι> R02 and R03 are each independently of the others halogen, nitro, cyano, d-C4alkyl, C2-C4alkenyl, C2-C4alkynyl, CrC4haloalkyl, C2-C6haloalkenyl, C3-C6cycloalkyl, halo- substituted C3-C6cycloalkyl, CrC6alkoxyalkyl, CrC6alkylthioalkyl, hydroxy, mercapto, d-C6alkoxy, C3-C6alkenyloxy, C3-C6alkynyIoxy, d-C alkylcarbonyl, d-C4alkoxycarbonyl, C C4alkylthio, CrC alkylsulfinyl, d-C4alkylsulfonyl, amino, CrC4alkylamino or di(d- C4alkyl)amino; R04 and R05 together are a group
-C-Rθ6(Rθ7)-O-C-Ro8(Rθ9)-C-Ro1θ(Rθ1l)-C-Ro12(Rθ13)" (Zi),
-C-Roi (Roi5)-C-Roi6(Roi7)"O-C-R0i8(Roi9)"C-Ro2o(Ro2i)- ( 2) or
-C-Rθ22(Rθ23)-C-Rθ24(Rθ25)"C-Rθ26( θ27)"O-C-Rθ28(Rθ29)- (Z3), wherein Roε, Ro7> Roe. R09, Roιo> Ron> R012, Roι3> Roι4. Roιs> Roi6> R017, Roιs> Roi9, Ro2o> Ro2i> R022, R023, Ro2 , Ro25, R026. R027, R028 and R029 are, each independently of the others, hydrogen, halogen, d-C4alkyl or d-C4haloalkyl, it being possible for an alkylene ring, which together with the carbon atoms of the group 7.Λ, Z2 or Z3 contains from 2 to 6 carbon atoms and which may be interrupted by oxygen, to be either fused or spiro-bound to the carbon atoms of the group Z1 ; Z2 or Z3 or that alkylene ring bridges at least one ring atom of the group Z^ Z≥ or Z3; G is hydrogen, -CfX -R∞o, -C(X2)-X3-R03i , -C(X4)-N(R032)-Ro33, -SO2-R034, an alkali metal cation, alkaline earth metal cation, sulfonium cation or ammonium cation or -P(X5)(Ro35)-Ro36; i, X2, 3, X4 and X5 are each independently of the others oxygen or sulfur; and Roso, R031, Ro32, R033, R034, Ross and R036 are each independently of the others hydrogen, d-C5aIkyl, d-C5haloalkyl, C2-C5alkenyl, d-C5alkoxyalkyl, C3-C6cycloalkyl or phenyl, and R034 may additionally be C2-C20alkenyl; C2-C20alkenyl substituted by halogen, d- C6alkylcarbonyl, Cι-C8alkoxycarbonyl, CrC6alkylcarbonyIoxy, CrC6alkoxy, d-Cethioalkyl, CrC6alkylthiocarbonyl, C C6alkylcarbonylthio, CrC6alkylsulfonyl, CrC6alkylsulfoxyl, d- C6alkylaminosulfonyl, CrC6(di)alkylaminosulfonyl, CrC6CrCe alkylsulfonyloxy, d-C6alkyl- sulfonylamino, CrC6alkylamino, CrC6(di)alkylamino, CrC6alkylcarbonylamino, di-d-C6 alkylcarbonylamino, CrC6alkylalkylcarbonylamino, cyano, (C3-C7)cycloalkyl, (C3- C7)heterocyclyl, tri-CrC6alkylsilyl, tri-CrC6alkylsilyloxy, phenyl or heteroaryl; or R03 is C2- C20alkynyl; C2-C20alkynyl substituted by halogen, d-C6alkylcarbonyl, CrC6 alkoxycarbonyl, CrC6alkylcarbonyloxy, CrC6alkoxy, CrC6thioalkyl, CrC6alkylthiocarbonyl, C C6alkylcarbonylthio, d-C6alkylsulfonyl, CrC6alkylsulfoxyl, CrC6alkylaminosulfonyl, di-d-C6 alkylaminosulfonyl, CrC6alkylsulfonyloxy, CrC6alkylsulfonylamino, CrC6alkylamino, di- C C6alkylamino, CrC6alkylcarbonylamino, di- Cι-C6alkylcarbonylamino, d- C6alkylcarbonylamino, cyano, (C3-C7)cycloalkyl, (C3-C7)heterocyclyl, tri-CrC6alkylsilyl, tri- d- C6alkylsilyloxy, phenyl or heteroaryl; or R03 is (d-C7)cycloalkyl; (d-C7)cycloalkyl substituted by halogen, haloalkyl, d-C6alkyl, CrC6alkoxy, CrC6 alkylcarbonyloxy, d- C6thioaIkyl, d-C6alkylcarbonylthio, CrC6alkylamino, CrC6alkylcarbonylamino, tri- d- C6alkylsilyl or by tri- d-C6alkylsilyloxy; or R034 is heteroaryl; heteroaryl substituted by halogen, CrCehaloalkyl, nitro, cyano, d-C6alkyl, CrC6alkoxy, d-C6alkylcarbonyloxy, d- C6thioalkyl, CrC6alkylcarbonylthio, CrC6alkylamino, CrC6alkylcarbonylamino, tri- d- C6alkylsilyl or by tri- d-C6alkylsilyloxy; heteroaryloxy, heteroarylthio, heteroarylamino, di- heteroarylamino, phenylamino, diphenylamino, C2-C6cycloalkylamino, di-C2- C6cycloalkylamino or C2-C6cycloalkoxy and salts and diastereoisomers of compounds of formula 2.52;
and the compound of formula 2.53
and the compounds prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P- ethyl, diclof op-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlorotoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, trifluralin, fluthiamide, isoxaben, triallate, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalof op-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin.
In the above formulae, "Me" is a methyl group.
The invention also includes the salts that the compounds of formula I are able to form with amines, alkali metal and alkaline earth metal bases or quaternary ammonium bases. Among the alkali metal and alkaline earth metal hydroxides used as salt formers, emphasis is to be given to the hydroxides of lithium, sodium, potassium, magnesium and calcium, but especially to those of sodium and potassium.
Examples of suitable amines for ammonium salt formation that come into consideration are ammonia as well as primary, secondary and tertiary d-C18alkylamines, d-C4hydroxyalkyl- amines and C2-C alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four butylamine isomers, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methyl-ethylamine, methyl-isopropylamine, methyl- hexylamine, methyl-nonylamine, methyl-pentadecylamine, methyl-octadecylamine, ethyl- butylamine, ethyl-heptylamine, ethyl-octylamine, hexyl-heptylamine, hexyl-octylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-n- amylamine, diisoamylamine, dihexylamine, diheptylamine, dioctylamine, ethanolamine, n-propanolamine, isopropanolamine, N,N-diethanolamine, N-ethylpropanolamine, N-butyl- ethanolamine, allylamine, n-butenyl-2-amine, n-pentenyl-2-amine, 2,3-dimethylbutenyl-2- amine, dibutenyl-2-amine, n-hexenyl-2-amine, propylenediamine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butyl- amine, tri-n-amylamine, methoxyethylamine and ethoxyethylamine; heterocyclic amines, for example pyridine, quinoline, isoquinoline, morpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary arylamines, for example anilines, methoxyanilines, ethoxyanilines, o-, m- and p-toluidines, phenylenediamines, benzidines, naphthylamines and o-, m- and p-chloroanilines; but especially triethylamine, isopropylamine and diisopropyl- amine.
Compounds of formula I wherein p is 0 are preferred.
Preference is given to compounds of formula I wherein
R, is -CH2-, -CH2CH2-, -CF2, -CH=CHCH2-, -CH(CH3)- or -C≡CCH2-, but especially -CH2-, in each case the left-hand free valency being attached to the pyridine ring.
Preference is also given to those compounds of formula I wherein X^ is oxygen, sulfonyl or a group -NR52SO2-, especially oxygen.
Of special interest are compounds of formula I wherein R2 is -CH2OCH3, -CH2OCH2CH3, -CH2CH2OCH3, -CH2CH2SO2CH3 or -CH2CH2OCH2CH2OCH3, preferably -CH2CH2OCH3, with prominence being given to those compounds wherein X^ is oxygen and Ri is -CH2-. In that group of compounds preference is given to those wherein Q is Qi and R13 is hydroxy.
Emphasis is also given to compounds of formula I wherein R2 is
en ° c„ OCH o cH GCH CcH (rCH° ( OH
. Where no free valency is indicated in the case of those preferred meanings of
CH
R2, for example in the case of , the attachment position is located at the carbon atom identified by "CH".
In a further preferred group of compounds of formula I, R3 is CF3, CF2CF3, CF2CI, CF2H or CCI3, especially CF3, R4 preferably being hydrogen or methyl, especially hydrogen. R6, R7, Rs, Rg, R10, R11, R12, R51 and R52 are each independently of the others especially hydrogen, d-C4alkyl, CrC6alkoxy-CrCealkyl, or CrC6alkoxy-CrC6alkyl substituted by d-C6alkoxy, while in addition, in a preferred group of compounds of formula I, Q is Q2 and Ri is methylene.
Very special preference is given to Q being Q^ and R13 being hydroxy or halogen, especially hydroxy. In that group of compounds, emphasis is to be given to those wherein a) A-, is C(R14Rι5) or NR16, and A2 is C(R17Rι8), C(O) or oxygen, or b) A-i is C(R14R15) and A2 is C(Rι7R18), and R14 and R22 together form a C2-C3alkylene chain, preferably an ethylene chain, R15, Rι7, R18 and R2ι being especially hydrogen; or c) A2 is C(O) or C(R17R18), A-, is C(R14R15), and R14, R15, R17 and R18 are each independently of the others hydrogen, methyl, ethyl, methoxycarbonyl or ethoxycarbonyl; or d) R14 and R15 together or R21 and R22 together form a C2alkylene chain (cyclopropyl ring), A2 is CH2, and R21 and R22, or R and R-ι5, are each independently of the other hydrogen, d-C4alkyl, methoxycarbonyl or ethoxycarbonyl; or e) A2 is C(R17Ri8) and A^ is C(Rι4R15), and R18 and R14 together form a C2-C3alkylene chain.
In a further group of compounds of formula I to which prominence is given, Q is Q3, R49 is cyclopropyl, and R50-S(O)n is methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl.
Preferred synergistic mixtures according to the invention comprise as active ingredients a compound of formula I and either the compound of formula 2.2.a Q
(2.2.a, aRS,1 'S(-)N-(1'-methyl-2'-methoxyethyl)-N-
chloroacetyl-2-ethyl-6-methylaniline), or the racemic compound of formula 2.2. b or the compound of formula 2.2 wherein R53 is ethyl, R54 is methyl and R55 is ethoxymethyl, or the compound of formula 2.2. wherein R53 is ethyl, R54 is ethyl and R55 is methoxymethyl, or a compound of formula 2.3, or a compound of formula 2.30, or a compound of formula 2.4, or a compound of formula 2.13, or the compound of formula 2.14, or the compound of formula 2.6 wherein R62 is hydrogen, Z is methine, R63 is methyl, Y is nitrogen, R64 is fluorine, R65 is hydrogen and R66 is fluorine or wherein R62 is methoxy, Z is methine, R63 is methoxy, Y is methine, R6 is chlorine, R6s is methyl and R66 is chlorine, or the compound of formula 2.7 wherein R67 is -C(O)-S-n-octyl, or a compound of formula 2.12, or the compound of formula 2.18, or the compound of formula 2.19, or the compound of formula 2.21 , or the compound of formula 2.25, or the compound of formula 2.33, or the compound of formula 2.45, or a compound of formula 2.1.
Especially preferred synergistic mixtures according to the invention comprise as active ingredients a compound of formula I and either the compound of formula 2.2.a
(2.2.a, aRS,1'S(-)N-(1 '-methyl-2'-methoxyethyl)-N-
chloroacetyl-2-ethyl-6-methylaniline), or the racemic compound of formula 2.2.b
or a mixture of the compounds of formulae 2.2. a and 2.2. b wherein the compound of formula 2.2.a is present in excess, preferably in a ratio by weight of from 2.5:1 to 3:1 , with respect to the compound of formula 2.2. b, or the compound of formula 2.2 wherein R53 is ethyl, R5 is methyl and R55 is ethoxymethyl, or the compound of formula 2.2 wherein R53 is ethyl, R54 is ethyl and R55 is methoxymethyl, or a compound of formula 2.3, or the compound of formula 2.30.
Further especially preferred synergistic mixtures according to the invention comprise as active ingredients a compound of formula I and a compound of formula 2.52a as indicated in Table 1 :
Table 1 : Compounds of formula 2.52a:
Comp. Rθ1 R, 02 R ',03 Phys. data
No.
1.001 CH3 CH3 CH3 H m.p. 245°C
1.002 CH3 CH3 CH3 C(O)C(CH3)3 m.p. 135- 136°C
1.003 CH3 CH3 CH3 C(O)OCH2CH3
1.004 CH2CH3 CH3 CH3 H m.p. 182- 185°C
1.005 CH2CH3 CH3 CH3 C(O)C(CH3)3 m.p. 110- 113°C
1.006 CH2CH3 CH3 CH3 C(O)OCH2CH3 1.007 CH2CH3 CH3 CH2CH3 H m.p. 189- 191 °C
1.008 CH2CH3 CH3 CH2CH3 C(O)C(CH3)3 m.p. 122- 124°C Comp. Rθ1 R 02 R 03 G Phys. data
No.
1.009 CH2CH3 CHa C(O)OCH2CH3 m.p.114-
116°C
1.010 CH=CH2 CHa CH, H m.p.165-
170°C
1.011 CH=CH2 CH3 CH, C(O)C(CH3)3 m.p.111-
113°C
1.012 CH=CH2 CH3 CH2CH3 H
1.013 CH=CH2 CH3 CH=CH2 H
1.014 CH=CH2 CH3 CH=CH2 C(O)C(CH3)3
1.015 C≡CH CH3 CH3 H m.p.179- 184°C
1.016 C≡CH CH3 CH3 C(O)C(CH3)3 m.p.109- 111°C
1.017 C≡CH CH3 CH3 C(O)OCH2CH3
1.018 C≡CH CH3 CH CH3 H m.p.189- 193°C
1.019 C≡CH CH3 CH2CH3 C(O)C(CH3)3
1.020 C≡CH CH3 CH2CH8 C(O)OCH2CH3
1.021 C≡CH CH3 C≡CH H m.p.300°C
1.022 C≡CH CH3 C≡CH C(O)C(CH3)3 m.p.183- 185°C
1.023 C≡CH CH3 C≡CH C(O)OCH2CH3
1.024 C≡CH CH3 CH=CH2 H
1.025 C≡CCH3 C CHH33 CH3 H m.p.179- 181°C
1.026 C≡CCH3 CH3 CH3 C(O)C(CH3)3 m.p.128- 129°C
1.027 C≡CCH3 CH3 CH3 C(O)OCH2CH3 1.028 C≡CCH3 CH3 CH2CH3 H 1.029 C≡CCH3 CH3 CH CH3 C(O)C(CH3)3 1.030 C≡CCH3 CH3 C≡CCH3 H Comp. R01 Rθ2 R 03 G Phys. data
No.
1.031 C≡CCHg CH3 C≡CCH3 C(O)C(CH3)3
1.032 CH2CH2CH3 CH3 CH3 H m.p. 136- 138°C
1.033 CH2CH2CH3 CH CH3 C(O)C(CH3)3 m.p. 65- 67°C
1.034 CH2CH2CH3 CH3 CH3 C(O)OCH2CH3
1.035 CH2CH2CH3 CH3 CH CH3 H
1.036 CH2CH2CH3 CH3 CH2CH2CH3 H
1.037 CH2CH2CH3 CH3 CH2CH2CH3 C(O)C(CH3)3
1.038 CH2CH2CH3 CH3 CH2CH2CH3 C(O)OCH2CH3
1.039 CH2CH2CH3 CH3 C≡CH H
1.040 CH(CH3)2 CH3 CH3 H m.p. 214- 216°C
1.041 CH(CH3)2 CH, CH3 C(O)C(CH3)3 m.p. 148- 151 °C
1.042 CH(CH3)2 CH3 CH2CH3 H
1.043 CH(CH3)2 CH3 C≡CH H
1.044 >- CH3 CH3 H
1.045 >- CH3 CH2CH3 H
1.046 CH3 C≡CH H
\>-
1.047 CH2CH=CH2 CH3 CH3 H
1.048 CH2CH=CH2 CH3 CH2CH3 H
1.049 CH2CH=CH2 CH3 C≡CH H
1.050 CH2CH2CH2CH3 CH3 CH3 H
1.051 CH2CH2CH2CH3 CH3 CH2CH3 H
1.052 N(CH2CH3)2 CH3 CH3 H
1.053 N(CH2CH3)2 CH3 CH2CH3 H
1.054 CH2OH CH3 CH3 H
1.055 CH2OCH3 CH3 CH3 H Comp. R01 R02 R03 G Phys. date
No.
1.056 CH2OC(CH3)3 CH3 CH3 H
1.057 CH3 CH2CH3 CH3 H
1.058 CH2CH3 CH2CH3 CH3 H
1.059 CH2CH3 CH2CH3 CH2CH3 H m.p. 185- 187°C
1.060 CH2CH3 CH2CH3 CH2CH8 C(O)C(CH3)3 m.p. 126- 128°C
1.061 CH2CH3 CH2CH8 CH2CH3 C(O)OCH2CH3 m.p. 105- 107°C
1.062 CH=CH2 CH2CH3 CH=CH2 H
1.064 CH3 CH=CH2 CH3 H
1.065 CH2CH3 CH=CH2 CH2CH3 H
1.066 CH2CH3 CH=CH2 CH3 H
1.067 CH2CH3 CH=CH2 CH3 C(O)C(CH3)3 m.p. 108- 110°C
1.068 C≡CH CH=CH2 C≡CH H
1.069 CH3 C≡CH CH3 H
1.070 CH CH3 C≡CH CH3 H m.p. 240- 243°C
1.071 CH2CH3 C≡CH CH3 C(O)C(CH3)3 m.p. 138- 140°C
1.072 CH2CH3 C≡CH CH3 C(O)OCH2CH3
1.073 CH CH3 C≡CH CH2CH3 H
1.074 CH2CH3 C≡CH C≡CH H
1.075 C≡CH C≡CH C≡CH H
1.076 CH3 CH2CH=CH2 CH3 H
1.077 CH3 CH2CH=CH2 CH2CH3 H
1.078 CH3 CH3 Br H m.p. 234- 237°C
1.079 CH3 CH3 Br C(O)C(CH3)3 m.p. 76- o o o o o o o o o o o o o o o o o o o o o o o O o o o o O o CO O co o O CO CO CO 00 00 00 CO 00 00 00 00 00 00
(33 cn 4^. CO ro o co 00 -J cn CO ro _- o O 00 --J C33 cn J-. co ro ->■ o 3
TJ
o - ro -, o j. o — o — o j. -π -π o o o o o o- rjd O O O CD 03 DO DO DO o o X ~ — — x x "" "■ X X x "• -• X X X
ro o o o o o
x x x x x x x x x x x x x x O
ro ro ^1 o 3 co 3 (33 3 ro O 3
— 00 "0
-X
Q. TJ o TJ CO T3 O TJ o o O O
O ro O ro
CO ro o ro
CJ3 o CO Q. 00 00 03
03
Comp. Rθ1 R02 Rθ3 G Phys. da1
No.
1.107 CH2CH3 Br CI H
1.108 CH2CH3 CI Br H
1.109 OCH3 CH3 CH3 H
1.110 OCH3 CH3 CH2CH3 H m.p. 178- 179°C
1.111 OCH3 CH3 CH2CH3 C(O)C(CH3)3 m.p. 146- 147°C
1.112 OCH3 CH3 CH2CH3 C(O)OCH2CH3
1.113 OCH3 CH3 CH CH2CH3 H
1.114 OCH3 CH3 C≡CH H
1.117 C(O)CH3 CH3 CH3 H solid
1.118 C(O)CH3 CH3 CH2CH3 H
1.119 CH3 C(O)CH3 CH2CH3 C(O)C(CH3)3 m.p. 163- 165°C
1.120 CH3 CH2OH CH2CH3 H
1.121 CH3 CH3 CH3 SO2CH2CHCH2
1.122 CH3 CH3 CH3 SO2CH2CHCHCI
1.123 CH3 CH3 CH3 SO2CH2CHCHCH3
1.124 CH2CH3 CH3 CH2CH3 SO2CH2CHCH2
1.125 CH2CH3 CH3 CH2CH3 SO2CH2CHCHCI
1.126 CH2CH3 CH3 CH2CH3 SO2CH2CHCHCH3
Combinations of the compounds of formula I with the compound of formula 2.2a (2.2a, aRS,1 'S(-)N-(1 '-methyl-2'-methoxyethyI)-N-
chloroacetyl-2-ethyl-6-methylaniline) have been found to be very especially effective compositions.
The Tables that follow list especially preferred compounds of formula I for the composition according to the invention.
In the Table that follows, the left-hand valency of the radical is attached to the pyridine ring. When no free valency is indicated in the case of the substituent R2, for example in the
CH case of the attachment position is located at the carbon atom identified by "CH".
In the Table that follows, the compounds of formula I are represented as follows:
A-Q
wherein formula A
denotes the following radicals: Radical Ri Ra R3 Xi P Radical Ri R2 R4 R3 i P
A1 CH2 CH3 H CF3 O 0
A2 CH2 CH2CH3 H CF3 O 0
A3 CH2 (CH3)2CH H CF3 O 0
A4 CH2 PhCH2 H CF3 O 0
A5 CH2 CH3 H CF3 s 0
A6 CH2 CH3 H CF3 SO 0
A7 CH2 CH3 H CF3 SO2 0
A8 CH2 CH3OCH2 H CF3 O 0
A9 CH2 CH3CH2OCH2 H CF3 O 0
A10 CH2 CH3OCH2CH2 H CF3 O 0
A11 CH2 CH3CH OCH CH2 H CF3 O 0
A12 CH2 CH3OC(CH3)2CH2 H CF3 O 0
A13 CH2 CH3OCH(CH3)CH2 H CF3 O 0
A14 CH2 CH3OCH2CH(CH3) H CF3 O 0
A15 CH2 CH3OCH2C(CH3)2 H CF3 O 0
A16 CH2 CH3OCH(CH3) H CF3 O 0
A17 CH2 CH3OC(CH3)2 H CF3 O 0
A18 CH2 HC≡CCH2 H CF3 O 0
A19 CH2 H2C=CHCH2 H CF3 O 0
A20 CH2 CH3C≡CCH2 H CF3 O 0
A21 CH2 [ H H CF3 O 0
A22 CH2 °pc„ H CF3 O 0
A23 CH2 H CF3 O 0
CCH
A25 CH2 H CF3 O 0
CCH
A26 CH2 H CF3 O 0 o— '
Radical Ri Xi
A29 CH, H CF3 O
O^ H
A30 CH2 H CF3 O
CH
Radical Ri R4 Xi
A40 CH2 H CF3 O
N I CH,
Radical Ri R2 R4 Xi
A58 CH2 o- -C1H, H CF3 O 0
A59 CH2 CH, H CF3 O 0 o.
A60 CH2 CH, H CF3 O 0
A61 CH2 CH, H CF3 O 0 o
Radical Ri R3 Xi
Radical R^ R2 R4 Xi
Radical Ri Xi
A117 CH2CH2 CH H CF3 O 0
A120 CH2CH2 H CF3 O 0
CL .CH
A121 CH2CH2 O H CF, O 0
CH
Radical R^ R2 R4 Xi
Radical Ri Xi P
A148 CH2CH o H CF3 O 0
L^ CH,
A149 CH2CH ^CH2 H CF3 O 0
A150 CH2CH2 CH, H CF3 O 0
O
A151 CH2CH2 CH, H CF3 O 0
A152 CH2CH CH, H CF3 O o
Radical R4 Xi
A156 CH 2,Cv_/Hπ2 H CF3 O 0
A164 CHpCH,
Radical Ri Xi
A179 CH2CH2 H CF3 O 0
> > > ro ro ro o o o n cn • >
O O O
X X X
O O O o o o
X X X o o o to X to X X
O O
Radical Ri R2 R4 R3 Xi P
_____ _________ ___ _ __ _ __
A208 CH(OCH3)CH2 /^CH H CF3 O 0
A209 CH(OCH3)CH2 H CF3 O 0
A210 CH(OCH3)CH2 H CF3 O 0
A211 CH(OCH3)CH2 /\ H CF3 O 0
0^,CH A212 CH(OCH3)CH2 Q^\ H CF3 O 0
,CH
A213 CH(OCH3)CH2 H CF3 O 0
A214 CH(OCH3)CH2 H CF3 O 0
A215 CH(OCH3)CH2 H CF3 O 0
A216 CH(OCH3)CH2 H CF3 O 0
A217 CH(OCH3)CH2 H CF3 O 0
A219 CH(OCH3)CH2 H CF3 O
Radical Ri R2 R4 R3 Xi P
_ _ _
A220 CH(OCH3)CH2
A221 CH(OCH3)CH2 H CF3 O
I CH3
A222 CH(OCH3)CH2 H CF3 O 0
A223 CH(OCH3)CH2 H CF3 O
A225 CH(OCH3)CH2 r^ ^ H CF3 O 0
A226 CH(OCH3)CH2 H CF3 O 0
A227 CH(OCH3)CH2 H CF3 O 0
A228 CH(OCH3)CH2 H CF3 O 0
A229 CH(OCH3)CH2 H CF3 O 0
A230 CH(OCH3)CH2 H CF3 O 0
A231 CH(OCH3)CH2 H CF3 O 0
Radical R4 Xi
A232 CH(OCH3)CH2 H CF3 O 0
A235 CH(OCH3)CH2 H CF3 O 0
A236 CH(OCH3)CH2 H CF3 O 0
A237 CH(OCH3)CH2 H CF3 O 0
A238 CH(OCH3)CH2 H CF3 O 0
A239 CH(OCH3)CH2 °>-CH2 H CF3 O 0
A240 CH(OCH3)CH2 ^CH2 H CF3 O 0
A241 CH(OCH3)CH2 CH, H CF3 O 0
O
A242 CH(OCH3)CH2 CH, H CF3 O 0
A243 CH(OCH3)CH2 CH, H CF3 O 0 o
A244 CH(OCH3)CH2 H CF3 O 0
A245 CH(OCH3)CH2 H CF3 O 0
Radical Ri R2 R R3 Xi p
A247 CH(OCH3)CH2 H CF3 O 0
° CHι
A248 CH(OCH3)CH2 H CF3 O 0
A249 CH(OCH3)CH2 CH! H CF3 O 0
A251 CH(OCH3)CH2 H CF3 O 0
A252 CH(OCH3)CH2 H CF3 O 0
A253 CH(OCH3)CH2 H CF3 O 0
A254 CH(OCH3)CH2 __/ CHs H CF3 O 0
A255 CH(OCH3)CH2 H CF3 O 0
A256 CH(OCH3)CH2 H CF3 O 0
A257 CH(OCH3)CH2 H CF3 O 0
Radical Ri R2 R4 R3 Xi p
A260 C CHH((OOCCHH33))CCHH22 H CF3 O 0
A261 C CHH((OOCCHH33))CCHH22 H CF3 O 0
A264 CCHH((OOCCHH33))CCHH22
A265 CCHH((OOCCHH33))CCHH22 H CF3 O
A266 CCHH((OOCCHH33))CCHH22
A267 CCHH((OOCCHH33))CCHH22 , CCHH22 H CF3 O 0
A268 CCHH((OOCCHH33))CCHH22 _ / ,CCHH22 H CF3 O 0
A269 CCHH((OOCCHH33))CCHH22
Radical Rή R2 R4 R3 Xi
A296 CH2CH(OCH3)CH2 /^CH H CF3 O~
A297 CH2CH(OCH3)CH2 ^CH H CF3 O 0
A298 CH2CH(OCH3)CH2 c^CH H CF3 O 0
A299 CH2CH(OCH3)CH2 /^r CHH H CF3 O 0 o-f A300 CH2CH(OCH3)CH2 H CF3 O 0
A301 CH2CH(OCH3)CH2 H CF3 O 0
A302 CH2CH(OCH3)CH2 /\ H CF3 O 0
O^/CH
A303 CH2CH(OCH3)CH2 0-- \ H CF3 O 0
CH
A304 CH2CH(OCH3)CH2 H CF3 O 0
A305 CH2CH(OCH3)CH2 H CF3 O 0
A306 CH2CH(OCH3)CH2 c . H CF3 O 0
A307 CH2CH(OCH3)CH2 H CF3 O
A308 CH2CH(OCH3)CH2 H CF3 O 0
A309 CH2CH(OCH3)CH2 H CF3 O 0
Radical Ri R2 R4 R3 Xi P
A311 CH2CH(OCH3)CH2 H CF3 O 0
A312 CH2CH(OCH3)CH2 H CF3 O 0
A313 CH2CH(OCH3)CH2 H CF3 O 0
A314 CH2CH(OCH3)CH2 r^ ^ H CF3 O 0
A315 CH2CH(OCH3)CH2 H CF3 O 0
A316 CH2CH(OCH3)CH2 f^ ^ H CF3 O 0
A317 CH2CH(OCH3)CH2 H CF3 O 0
A318 CH2CH(OCH3)CH2 H CF3 O
A319 CH2CH(OCH3)CH2 H CF3 O
A320 CH2CH(OCH3)CH2 H CF3 O
A321 CH2CH(OCH3)CH2 H CF3 O
Radical R4 Xi
A323 CH2CH(OCH3)CH2 H CF3 O
A324 CH2CH(OCH3)CH2 H CF3 O 0
A325 CH2CH(OCH3)CH2 H CF3 O
A326 CH2CH(OCH3)CH2 H CF3 O 0
A327 CH2CH(OCH3)CH2 H CF3 O
A328 CH2CH(OCH3)CH2 H CF3 O
A329 CH2CH(OCH3)CH2 H CF3 O 0
A330 CH2CH(OCH3)CH2 O. H CF3 O 0
A331 CH2CH(OCH3)CH2 H CF3 O 0
A332 CH2CH(OCH3)CH2 -CH, H CF3 O 0
A333 CH2CH(OCH3)CH2 -CH, H CF3 O 0
A334 CH2CH(OCH3)CH2 -CH, H CF3 O 0
A335 CH2CH(OCH3)CH2 H CF3 O Radical Ri R2 R4 R3 Xi p
A337 CH2CH(OCH3)CH2 H CF3 O
A338 CH2CH(OCH3)CH2 H CF3 O 0
A339 CH2CH(OCH3)CH2 H CF3 O
A340 CH2CH(OCH3)CH2 H CF3 O 0
A341 CH2CH(OCH3)CH2 H CF3 O 0
A342 CH2CH(OCH3)CH2 H CF3 O 0
A343 CH2CH(OCH3)CH2 H CF3 O
A344 CH2CH(OCH3)CH2 H CF3 O 0
A345 CH2CH(OCH3)CH2 _ / C 2 H CF3 O 0
A346 CH2CH(OCH3)CH2 H CF3 O 0
A347 CH2CH(OCH3)CH2 H CF3 O 0
Radical Ri R2 R4 R3 Xi p
A348 CH2CH(OCH3)CH2 H CFg" O 0~
A349 CH2CH(OCH3)CH2 H CF3 O 0
A350 CH2CH(OCH3)CH2 H CF3 O 0
A351 CH2CH(OCH3)CH2 H CF3 O 0
A352 CH2CH(OCH3)CH2 H CF3 O 0
A353 CH2CH(OCH3)CH2 H CF3 O 0
A354 CH2CH(OCH3)CH2 H CF3 O 0
A355 CH2CH(OCH3)CH2 H CF3 O 0
A356 CH2CH(OCH3)CH2 ocH3 H CF3 O 0
A357 CH2CH(OCH3)CH2 O H CF3 O 0 rγCH!
A358 CH2CH(OCH3)CH2 H CF3 O 0
A359 CH2CH(OCH3)CH2 __/ CHa H CF3 O 0 ft N O'
Radical Ri Xi
A386 CH=CHCH2 ° CH H CF3 O 0
A387 CH=CHCH2 CH H CF3 O 0
A388 CH=CHCH2 ^CH H CF3 O 0 O^
A389 CH=CHCH2 CH H CF3 O 0
A390 CH=CHCH2 CH H CF3 O
A393 CH=CHCH2 H CF3 O 0
O^^CH
A395 CH=CHCH2 ^ H CF3 O 0
V0H
Radical Ri R2 Xi
A404 CH=CHCH2 O H CF3 O 0
N I^ CH,
Radical Ri Xi P
A421 CH=CHCH2 °^CH2 H CF3 O 0
A422 CH=CHCH2 Λ^CH2 H CF3 O 0
A423 CH=CHCH2 CH, H CF3 O 0
O
A424 CH=CHCH2 /^CH, H CF3 O 0
A425 CH=CHCH2 ^N^CH2 H CF3 O 0 o—l Radical Ri R2 R4 R3 Xi
A429 C CHH==CCHHCCHH22 H CF3 O 0
A431 C CHH==CCHHCCHH22 /^ -CH2 H CF3 O
UYCHS
A432 C CHH==CCHHCCHH22 H CF3 O 0
A433 CCHH==CCHHCCHH22 H CF3 O
A434 CCHH==CCHHCCHH22 H CF3 O
A435 CCHH==CCHHCCHH22 H CF3 O
A436 CCHH==CCHHCCHH22 , CCHH22 H CF3 O
A437 CCHH==CCHHCCHH22 0 H CF3 O
Radical R2 R. R3
A445 CH=CHCH2 H CF3 O 0
Radical Ri R4 R3 Xi P
A472 C≡CCH2 CH3OC(CH3)2 H CF3 O T
A473 C≡CCH2 HC≡CCH2 H CF3 O o
A474 C≡CCH2 H2C=CHCH2 H CF3 O o
A475 C≡CCH2 CH3C≡CCH2 H CF3 O o
A476 C≡CCH2 H CF3 O 0
A479 C≡CCH2 /^CH H CF3 O 0
A481 C≡CCH2 CH H CF3 O 0
A484 C≡CCH2 H CF3 O 0
O^ H
A485 C≡CCH2 O' H CF3 O 0
CH
Radical Ri Xi
Radical Ri R2
A501 C≡CCH2 OCH, H CF3 O 0
&
A512 C≡CCH2 O
1>-CH2 H CF3 O 0 Radical Ri R2 R R3 Xi p
A517 C≡CCH2 /^/CH2 H CF3 O 0
Radical Ri R4 R_ Xi
A531 C≡CCH, -CH, H CF3 O 0
I
■M
A533 C≡CCH2 H CF3 O 0
Radical Ri R2 R4 R3 Xi P
A560 CH2 CH3OCH2CH(CH3) H CF2CI O 0
A561 CH2 CH3OCH2C(CH3)2 H CF2CI O 0
A562 CH2 CH3OCH(CH3) H CF2CI O 0
A563 CH2 CH3OC(CH3)2 H CF2CI O 0
A564 CH2 HC≡CCH2 H CF2CI O 0
A565 CH2 H C=CHCH2 H CF2CI O 0
A566 CH2 CH3C≡CCH H CF2CI O 0
A567 CH2 |>H H CF2CI O 0
A568 CH2 ° CH H CF2CI O 0
A569 CH2 CCH H CF2CI O 0
A570 CH2 ^CH H CF2CI O 0
A571 CH2 Cr H CF2CI O 0
A572 CH2 0" H CF2CI O 0
A574 CH2 H CF2CI O 0
VCH
A577 CH2 H CF2CI O 0
Radical R R2 R4 Xi
A580 CH, H CFPCI O
Radical RΛ R3 Xi
A600 CH,
Radical Ri R2 R R3 Xi
_____ __ ° -CH2 H CF2CI O "
A606 CH2 /\^CH2 H CF2CI O 0
A607 CH2 /\^CH2 H CF2CI O 0 o—l
Radical Ri
A624 CH2 CH, H CF2CI O 0
A627 CH, ocH3 H CF2CI O 0
CH,
N
&
> > > > > > > > > > > > > > > >
0) 0) 0) 0) 0) 0) 0) 0) 0) 0) 0) cn cn cn O) O) 4_ 4_ 4- 4- 4- 4_ 4-. 4_ CO CO CO CO CO O CO co s| 0) n ^ Cu M -' O (D C0 N| (33 n 4s. o ro
Ox Ox Ox Ox Ox Ox Ox Ox Ox Ox Ox o o o o o
X X X X X ro to ro ro
x x x x x x x x x x x o o o o o o T| o T| o T| o x x ox o tTI x ox ox ox o TI o T| ro to to
TI TI o rToI x x xTI x to to roTI roTI roTI toTI wTI to toTI o o o o o
O O O O O O CO O O O O
o o o o o o o o o o o
Radical Ri R2 R4 R3 Xi P
A648 CH2 CH3OC(CH3)2CH2 H CHF2 O 0
A649 CH2 CH3OCH(CH3)CH2 H CHF2 O 0
A650 CH2 CH3OCH2CH(CH3) H CHF2 O 0
A651 CH2 CH3OCH2C(CH3)2 H CHF2 O 0
A652 CH2 CH3OCH(CH3) H CHF2 O 0
A653 CH2 CH3OC(CH3)2 H CHF2 O 0
A654 CH2 HC≡CCH2 H CHF2 O 0
A655 CH2 H2C=CHCH2 H CHF2 O 0
A656 CH2 CH3C≡CCH2 H CHF2 O 0
A660 CH2 ^CH H CHF2 O 0
A661 CH2 " H CHF2 O 0
A662 CH2 H CHF2 O 0
0CH
A667 CH2 H CHF2 O 0
VCH Radical Ri Xi
A677 CH2 f^ ' H CHp2 ° °
A679 CH2 f^ ^ H C ?Z ° ° Radical Ri R2 R4 R3 Xi
Radical R R3 Xi
A692 CH2 |^CH2 H CHF2 O 0
A694 CH2 ^CH2 H CHF2 O 0
A695 CH2 CH, H CHF2 O 0
O
A696 CH2 CH, H CHF2 O 0
A697 CH2 CH, H CHF2 O 0 o
Radical Ri Xi
A714 CH, T CH'2, H CHF2 O 0
Radical Ri Xi
A718 CH, OH H CHF2 O 0
A725 CH, ,OCH2CH2 H CHF2 O
OCH,
A727 CH2 CH3 H CF3 O 1
A728 CH2 CH2CH3 H CF3 O 1
A729 CH2 (CH3)2CH H CF3 O 1
A730 CH2 PhCH2 H CF3 O 1
A731 CH2 CH3 H CF3 S 1
A732 CH2 CH3 H CF3 SO 1
A733 CH2 CH3 H CF3 SO2 1
A734 CH2 CH3OCH2 H CF3 O 1 Radical Ri R2 Xi
A735 CH2 CH3CH2OCH2 H CF3 O A736 CH2 CH3OCH2CH2 H CF3 O A737 CH2 CH3CH2OCH2CH2 H CF3 O A738 CH2 CH3OC(CH3)2CH2 H CF3 O A739 CH2 CH3OCH(CH3)CH2 H CF3 O A740 CH2 CH3OCH2CH(CH3) H CF3 O A741 CH2 CH3OCH2C(CH3)2 H CF3 O A742 CH2 CH3OCH(CH3) H CF3 O A743 CH2 CH3OC(CH3)2 H CF3 O A744 CH2 HC≡CCH2 H CF3 O
A745 CH2 H2C=CHCH2 H CF3 O A746 CH2 CH3C≡CCH2 H CF3 O
A747 CHs [ H H CF3 O
A749 CH2 H CF3 O
0CH
A750 CH2 ev H CF3 O
OsV
A751 CH2 r H CF3 O
A752 CH2 CH H CF3 O
A756 CH, O H CF3 O
CH Radical Ri R2 R4 R3 Xi
Radical Ri R2 Ra R3 Xi
Radical Ri R3 Xi
A783 CH2 °>-CH2 H CF3 O 1
A784 CH2 ^CH2 H CF3 O 1
A785 CH2 CH, H CF3 O 1
O.
A786 CH2 CH, H CF3 O 1
A787 CH2 CH, H CF3 O o
Radical RΪ R4 Xi
A802 CH, 0Hz H CF3 O
Radical R4 Xi
A817 CH2 CH3SCH2CH2 H CF3 O 0
A818 CH2 CH3SOCH2CH2 H CF3 O 0
A819 CH2 CHsSO2CH2CH2 H CF3 O 0
Radical i R2 R4 R3 Xi P
A843 CH2 n-heptyl-C(O) H CF3 O 0
A844 CH2 phenyl-C(O) H CF3 O 0
A845 CH2 CF3CH OCH2CHa H CF3 O 0
A846 CH2 CH3OCH2CH2CH2 H CF3 O 0
A847 CH2 HOCH CH2CH2 H CF3 O 0
A849 CH2 N≡CCH2CH2 H CF3 O 0
A850 CH2 CICH2CH2 H CF3 O 0
A851 CH2 H CF3 O 0
< CH
A852 CH2 H CF3 O
CH,
A853 CH2 CH3OCH2C(Br)HCH2 H CF3 O 0 A854 CH2 cv H CF3 O 0
CH,
A856 CH2 HOCH2CH2 H CF3 O 0
A858 CH2 CH3(OCH2CH2)3 H CF3 O 0
A859 CH2 CH3CH2OC(CH3)HOCH2CH2 H CF3 O 0
A860 CH2 n-heptyl-C(O)OCH2CH2 H CF3 O 0
A861 CH2 CH3C(O)OCH2CH2 H CF3 O 0
A862 CH2 CH3SO2OCH2CH2 H CF3 O 0
A863 CH2 H
C ^, CF3 O 0
A864 CH2 CH3 H CF3 -NCH3SO2- 0
A865 CH2 HOCH2C(OH)HCH2 H CF3 O 0
A866 CH2 phenyl-C(O)OCH2CH2 H CF3 O 0 Radical Ri R2 R4 R3 X P
A867 CH2 tert-butyl-C(O)OCH2CH2 H CF3 O 0 A868 CH2 CH3OC(O)CH2 H CF3 O 0
In the Table that follows, when the substituents Ai and A2 are rings the ring attachment he positions are at the carbon atom identified by "C", for example ^ ; in the case of open-
chain structures, "(CH3)2C", for example, is H,C
Q in the formula A-Q denotes Qi
and Qi denotes the following radicals B:
Radical Ai A2 n R21 R22 Rι3
B1 CH2 CH2 0 H H OH
B2 CH2 CH2 0 CH3 H OH
B3 CH2 CH2 0 CH3 CH3 OH
B4 (CH3)CH CH2 0 CH3 CH3 OH
B5 (CH3)2C CH2 0 CH3 CH3 OH
B6 CH CH 0 CH3 - OH
B7 CH2 CH2 0 CH3 CH2=CHCH2 OH
B8 CH2 CH2 0 CH3 HC≡CCH2 OH
B11 CH2 CH2 0 CH3 CH3SO2 OH Radical Ai A2 n R2ι R22 Rι3
B12 CH2 CH2 0 CH3 CH3O OH
B13 CH2 CH2 0 CH3 CH3OC(O) OH
B14 CH2 CH2 0 CH3 CH3CH2OC(O) OH
B15 CH2 (CH3)2C 0 H H OH
B16 o CH2 0 H H OH
B17 O CH2 0 H H OH
B18 o CH2 0 CH3 H OH
B19 t» CH2 0 CH3 CH3 OH
B20 CH2 0 H H OH
O
B21 C° CH2 0 CH3 H OH
B23 (CH3)2C O 0 CH3 CH3 OH
B24 CH2 O 0 CH3 CH3 OH
B25 CH3N O 0 CH3 CH3 OH
B26 -N O 0 CH3 CH3 OH
B27 CH3N CH2 0 CH3 CH3 OH
B28 CH3N (CH3)CH 0 H H OH
B29 CH3N (CH3)CH 0 CH3 H OH
B30 NH (CH3)C 0 H - OH
B31 NH CH 0 CH3 - OH
B32 CH3N (CH3)C 0 H - OH
B33 CH3N CH 0 CH3 - OH
B34 O (CH3)2C 0 H - OH
B35 O (CH3)2C 0 CH3 CH3 OH
B36 O (CH3)2C 0 CH3 H OH
B37 O (CH3)C 0 H - OH
B38 O CH 0 CH3 - OH Radical Ai n R 21 2-.2 M3
B39 (CH3)2C C=O 0 CH3 CH3 OH
B40 (CH3)2C (OH)CH 0 CH3 CH3 OH
B41 C=O 0 CH3 CH3 OH
>
B42 C=O 0 CH2 CH2 OH
B44 (CH3)2C CH3Oχ 0 CH3 CH3 OH CHgO^C
B47 (CH3)2C HON=C 0 CH3 CH3 OH
B48 (CH3)2C CH3ON=C 0 CH3 CH3 OH
B49 (CH3)2C BnON=C 0 CH3 CH3 OH
B50 CH O H CH2 OH
B51 CH C=O H CH2 OH
B52 CH CH2 H CH2 OH
B53 CH CH3N H CH2 OH
B54 CH CH2CH2 H CH2 OH
B55 CH C=O 2 H CH2 OH
B56 CH CH2 2 H CH2 OH
B57 CH CH2 H CH2 CI
B58 CH CH2 H CH2 NH2
B59 CH CH2 H CH2 CH3SO2NH
B60 CH CH2 H CH2 CH3OCH2CH2S
B61 CH CH2 H CH2 CH3OCH2CH2SO
B62 CH CH2 H CH2 CH3OCH2CH2SO2
B63 CH CH2 H CH2 (CH3)2NC(O)NH
B64 CH CH2 H CH2 PhC(O)O
B65 CH CH2 H CH2 CH3OC(O)O
Radical Ai 21 V22 '13
B93 (CH3)2C CH2 0 H H CI
B94 (CH3)2C CH2 0 H H NH2
B96 (CH3)2C CH2 0 H H CH3OCH2CH2S
B97 (CH3)2C CH2 0 H H CH3OCH2CH2SOJ
B98 (CH3)2C CH2 0 H H CH3OCH2CH2SO2
B99 (CH3)2C CH2 0 H H (CH3)2NC(O)NH
B100 (CH3)2C CH2 0 H H PhC(O)O
B101 (CH3)2C CH2 0 H H CH3OC(O)O
B102 (CH3)2C CH2 0 H H CH3(CH2)7S
B103 (CH3)2C CH2 0 H H CH3(CH2)7SO
B104 (CH3)2C CH2 0 H H CH3(CH2)7SO2
B105 (CH3)2C CH2 0 H H (CH3)2NSO2NH
B106 (CH3)2C CH2 0 H H PhS
B107 (CH3)2C CH2 0 H H PhSO
B108 (CHs)2C CH2 0 H H PhSO2
B11 1 CH2 (CH3)CH 0 H H OH
B112 CH2 CH2 1 H CH2 tert-butyl-C(O)O
B113 CH2 CH2 1 H CH2 tert-heptyl-C(O)O
or Q in the formula A-Q denotes Q2
and Q2 denotes the following radicals C:
Radical R34 R35 R36
C28 H CH3 CH3SO2O
C29 H CH3 p-tolylSO2O
or Q in the formula A-Q denotes Q3
and Q3 denotes the following radicals D (attachment position of R49 to the heterocycle is the group "CH"):
Radical R49 R50 n
D1 [ H CH3 0
D2 [ H CH3 1
D3 [ H CH3 2
D4 [ H CF3 0
D6 [ H CF3 2
D7 [ H Ph 0
D8 [ H Ph 1
D9 [ H Ph 2
D10 [ H PhCH2 0 Radical R49 R 50
D11 Γ^CH PhCH2 1
D12 r^CH PhCH2 2
Table 2: Compounds of formula I, represented as compounds of formula
A-Q
wherein Q is Q^ and Qi is the radical B52:
B52 B52 B52 B52 B52 B52 B52 B52 B52 B52 B52 B52~
A1 A2 A3 A4 A5 A6 A7 A18 A19 A20 A21 A22 A23 A24
A25 A26 A27 A28 A29 A30 A31 A32 A33 A34 A35 A36
A37 A38 A39 A40 A41 A42 A43 A44 A45 A46 A47 A48
A49 A50 A51 A52 A53 A54 A55 A56 A57 A58 A59 A60
A61 A62 A63 A64 A65 A66 A67 A68 A69 A70 A71 A72
A73 A74 A75 A76 A77 A78 A79 A80 A81 A82 A83 A84
A85 A86 A87 A88 A89 A90 A91 A92 A93 A94 A95 A96
A97 A98
A109 A110 A111 A112 A113 A114 A115 A116 A117 A118 A119 A120
A121 A122 A123 A124 A125 A126 A127 A128 A129 A130 A131 A132
A133 A134 A135 A136 A137 A138 A139 A140 A141 A142 A143 A144
A145 A146 A147 A148 A149 A150 A151 A152 A153 A154 A155 A156
A157 A158 A159 A160 A161 A162 A163 A164 A165 A166 A167 A168
A169 A170 A171 A172 A173 A174 A175 A176 A177 A178 A179 A180
A181 A182 A183 A184 A185 A186 A187 A188 A189 A200 A201 A202 A203 A204
A205 A206 A207 A208 A209 A210 A211 A212 A213 A214 A215 A216
A217 A218 A219 A220 A221 A222 A223 A224 A225 A226 A227 A228
A229 A230 A231 A232 A233 A234 A235 A236 A237 A238 A239 A240 B52 B52 B52 B52 B52 B52 B52 B52 B52 B52 B52 B52
A241 A242 A243 A244 A245 A246 A247 A248 A249 A250 A251 A252
A253 A254 A255 A256 A257 A258 A259 A260 A261 A262 A263 A264
A265 A266 A267 A268 A269 A270 A271 A272 A273 A274 A275 A276
A277 A278 A279 A280
A291 A292 A293 A294 A295 A296 A297 A298 A299 A300
A301 A302 A303 A304 A305 A306 A307 A308 A309 A310 A311 A312
A313 A314 A315 A316 A317 A318 A319 A320 A321 A322 A323 A324
A325 A326 A327 A328 A329 A330 A331 A332 A333 A334 A335 A336
A337 A338 A339 A340 A341 A342 A343 A344 A345 A346 A347 A348
A349 A350 A351 A352 A353 A354 A355 A356 A357 A358 A359 A360
A361 A362 A363 A364 A365 A366 A367 A368 A369 A370 A371
A382 A383 A384
A385 A386 A387 A388 A389 A390 A391 A392 A393 A394 A395 A396
A397 A398 A399 A400 A401 A402 A403 A404 A405 A406 A407 A408
A409 A410 A411 A412 A413 A414 A415 A416 A417 A418 A419 A420
A421 A422 A423 A424 A425 A426 A427 A428 A429 A430 A431 A432
A433 A434 A435 A436 A437 A438 A439 A440 A441 A442 A443 A444
A445 A446 A447 A448 A449 A450 A451 A452 A453 A454 A455 A456
A457 A458 A459 A460 A461 A462
A473 A474 A475 A476 A477 A478 A479 A480
A481 A482 A483 A484 A485 A486 A487 A488 A489 A490 A491 A492
A493 A494 A495 A496 A497 A498 A499 A500 A501 A502 A503 A504
A505 A506 A507 A508 A509 A510 A511 A512 A513 A514 A515 A516
A517 A518 A519 A520 A521 A522 A523 A524 A525 A526 A527 A528
A529 A530 A531 A532 A533 A534 A535 A536 A537 A538 A539 A540
A541 A542 A543 A544 A545 A546 A547 A548 A549 A550 A551 A552
A553 A564
A565 A566 A567 A568 A569 A570 A571 A572 A573 A574 A575 A576
A577 A578 A579 A580 A581 A582 A583 A584 A585 A586 A587 A588
A589 A590 A591 A592 A593 A594 A595 A596 A597 A598 A599 A600
A601 A602 A603 A604 A605 A606 A607 A608 A609 A610 A611 A612
A613 A614 A615 A616 A617 A618 A619 A620 A621 A622 A623 A624
A625 A626 A627 A628 A629 A630 A631 A632 A633 A634 A635 A636 B52 B52 B52 B52 B52 B52 B52 B52 B52 B52 B52 B52
A637 A638 A639 A640 A641 A642 A643
A654 A655 A656 A657 A658 A659 A660
A661 A662 A663 A664 A665 A666 A667 A668 A669 A670 A671 A672
A673 A674 A675 A676 A677 A678 A679 A680 A681 A682 A683 A684
A685 A686 A687 A688 A689 A690 A691 A692 A693 A694 A695 A696
A697 A698 A699 A700 A701 A702 A703 A704 A705 A706 A707 A708
A709 A710 A711 A712 A713 A714 A715 A716 A717 A718 A719 A720
A721 A722 A723 A724 A725 A726 A727 A728 A729 A730 A731 A732
A733 A744
A745 A746 A747 A748 A749 A750 A751 A752 A753 A754 A755 A756
A757 A758 A759 A760 A761 A762 A763 A764 A765 A766 A767 A768
A769 A770 A771 A772 A773 A774 A775 A776 A777 A778 A779 A780
A781 A782 A783 A784 A785 A786 A787 A788 A789 A790 A791 A792
A793 A794 A795 A796 A797 A798 A799 A800 A801 A802 A803 A804
A805 A806 A807 A808 A809 A810 A811 A812 A813 A814 A815 A816
A817 A818 A819 A820 A821 A822 A823 A824 A825 A826 A827 A828
A829 A830 A831 A832
Table 3: Compounds of formula I, represented as compounds of formula
A-Q
wherein Q is Qi, and Qi is the radical B39:
B39 B39 B39 B39 B39 B39 B39 B39 B39 B39 B39 B39
A1 A2 A3 A4 A5 A6 A7
A18 A19 A20 A21 A22 A23 A24
A25 A26 A27 A28 A29 A30 A31 A32 A33 A34 A35 A36
A37 A38 A39 A40 A41 A42 A43 A44 A45 A46 A47 A48
A49 A50 A51 A52 A53 A54 A55 A56 A57 A58 A59 A60
A61 A62 A63 A64 A65 A66 A67 A68 A69 A70 A71 A72
A73 A74 A75 A76 A77 A78 A79 A80 A81 A82 A83 A84
A85 A86 A87 A88 A89 A90 A91 A92 A93 A94 A95 A96
A97 A98
A109 A110 A111 A112 A113 A114 A115 A116 A117 A118 A119 A120
A121 A122 A123 A124 A125 A126 A127 A128 A129 A130 A131 A132
A133 A134 A135 A136 A137 A138 A139 A140 A141 A142 A143 A144
A145 A146 A147 A148 A149 A150 A151 A152 A153 A154 A155 A156
A157 A158 A159 A160 A161 A162 A163 A164 A165 A166 A167 A168
A169 A170 A171 A172 A173 A174 A175 A176 A177 A178 A179 A180
A181 A182 A183 A184 A185 A186 A187 A188 A189
A200 A201 A202 A203 A204
A205 A206 A207 A208 A209 A210 A211 A212 A213 A214 A215 A216
A217 A218 A219 A220 A221 A222 A223 A224 A225 A226 A227 A228
A229 A230 A231 A232 A233 A234 A235 A236 A237 A238 A239 A240
A241 A242 A243 A244 A245 A246 A247 A248 A249 A250 A251 A252
A253 A254 A255 A256 A257 A258 A259 A260 A261 A262 A263 A264
A265 A266 A267 A268 A269 A270 A271 A272 A273 A274 A275 A276
A277 A278 A279 A280
A291 A292 A293 A294 A295 A296 A297 A298 A299 A300 B39 B39 B39 B39 B39 B39 B39 B39 B39 B39 B39 B39
A301 A302 A303 A304 A305 A306 A307 A308 A309 A310 A311 A312
A313 A314 A315 A316 A317 A318 A319 A320 A321 A322 A323 A324
A325 A326 A327 A328 A329 A330 A331 A332 A333 A334 A335 A336
A337 A338 A339 A340 A341 A342 A343 A344 A345 A346 A347 A348
A349 A350 A351 A352 A353 A354 A355 A356 A357 A358 A359 A360
A361 A362 A363 A364 A365 A366 A367 A368 A369 A370 A371
A382 A383 A384
A385 A386 A387 A388 A389 A390 A391 A392 A393 A394 A395 A396
A397 A398 A399 A400 A401 A402 A403 A404 A405 A406 A407 A408
A409 A410 A411 A412 A413 A414 A415 A416 A417 A418 A419 A420
A421 A422 A423 A424 A425 A426 A427 A428 A429 A430 A431 A432
A433 A434 A435 A436 A437 A438 A439 A440 A441 A442 A443 A444
A445 A446 A447 A448 A449 A450 A451 A452 A453 A454 A455 A456
A457 A458 A459 A460 A461 A462
A473 A474 A475 A476 A477 A478 A479 A480
A481 A482 A483 A484 A485 A486 A487 A488 A489 A490 A491 A492
A493 A494 A495 A496 A497 A498 A499 A500 A501. A502 A503 A504
A505 A506 A507 A508 A509 A510 A511 A512 A513 A514 A515 A516
A517 A518 A519 A520 A521 A522 A523 A524 A525 A526 A527 A528
A529 A530 A531 A532 A533 A534 A535 A536 A537 A538 A539 A540
A541 A542 A543 A544 A545 A546 A547 A548 A549 A550 A551 A552
A553 A564
A565 A566 A567 A568 A569 A570 A571 A572 A573 A574 A575 A576
A577 A578 A579 A580 A581 A582 A583 A584 A585 A586 A587 A588
A589 A590 A591 A592 A593 A594 A595 A596 A597 A598 A599 A600
A601 A602 A603 A604 A605 A606 A607 A608 A609 A610 A611 A612
A613 A614 A615 A616 A617 A618 A619 A620 A621 A622 A623 A624
A625 A626 A627 A628 A629 A630 A631 A632 A633 A634 A635 A636
A637 A638 A639 A640 A641 A642 A643
A654 A655 A656 A657 A658 A659 A660
A661 A662 A663 A664 A665 A666 A667 A668 A669 A670 A671 A672
A673 A674 A675 A676 A677 A678 A679 A680 A681 A682 A683 A684
A685 A686 A687 A688 A689 A690 A691 A692 A693 A694 A695 A696 B39 B39 B39 B39 B39 E339 B39 B39 Ug §39 §39 B39
A697 A698 A699 A700 A701 A702 A703 A704 A705 A706 A707 A708
A709 A710 A711 A712 A713 A714 A715 A716 A717 A718 A719 A720
A721 A722 A723 A724 A725 A726 A727 A728 A729 A730 A731 A732
A733 A744
A745 A746 A747 A748 A749 A750 A751 A752 A753 A754 A755 A756
A757 A758 A759 A760 A761 A762 A763 A764 A765 A766 A767 A768
A769 A770 A771 A772 A773 A774 A775 A776 A777 A778 A779 A780
A781 A782 A783 A784 A785 A786 A787 A788 A789 A790 A791 A792
A793 A794 A795 A796 A797 A798 A799 A800 A801 A802 A803 A804
A805 A806 A807 A808 A809 A810 A811 A812 A813 A814 A815 A816
A817 A828
A829 A830 A831 A832 - -
Table 4: Compounds of formula I. represented as compounds of formula
A-Q
wherein Q is Qi, and Qi is the radical B3:
B3 B3 B3 B3 B3 B3 B3 B3 B3 B3 B3 B3
A18 A19 A20 A21 A22 A23 A24
A25 A26 A27 A28 A29 A30 A31 A32 A33 A34 A35 A36
A37 A38 A39 A40 A41 A42 A43 A44 A45 A46 A47 A48
A49 A50 A51 A52 A53 A54 A55 A56 A57 A58 A59 A60
A61 A62 A63 A64 A65 A66 A67 A68 A69 A70 A71 A72
A73 A74 A75 A76 A77 A78 A79 A80 A81 A82 A83 A84
A85 A86 A87 A88 A89 A90 -
A109 A110 A111 A112 A113 A114 A115 A116 A117 A118 A119 A120 A121 A122 A123 A124 A125 A126 A127 A128 A129 A130 A131 A132 B3 B3 B3 B3 B3 B3 B3 B3 B3 B3 B3 B3
A133 A134 A135 A136 A137 A138 A139 A140 A141 A142 A143 A144
A145 A146 A147 A148 A149 A150 A151 A152 A153 A154 A155 A156
A157 A158 A159 A160 A161 A162 A163 A164 A165 A166 A167 A168
A169 A170 A171 A172 A173 A174 A175 A176 A177 A178 A179 A180
A181 A182 A183 A184 A185 A186 A187 A188 A189
A200 A201 A202 A203 A204
A205 A206 A207 A208 A209 A210 A211 A212 A213 A214 A215 A216
A217 A218 A219 A220 A221 A222 A223 A224 A225 A226 A227 A228
A229 A230 A231 A232 A233 A234 A235 A236 A237 A238 A239 A240
A241 A242 A243 A244 A245 A246 A247 A248 A249 A250 A251 A252
A253 A254 A255 A256 A257 A258 A259 A260 A261 A262 A263 A264
A265 A266 A267 A268 A269 A270 A271 A272 A273 A274 A275 A276
A277 A278 A279 A280
A291 A292 A293 A294 A295 A296 A297 A298 A299 A300
A301 A302 A303 A304 A305 A306 A307 A308 A309 A310 A311 A312
A313 A314 A315 A316 A317 A318 A319 A320 A321 A322 A323 A324
A325 A326 A327 A328 A329 A330 A331 A332 A333 A334 A335 A336
A337 A338 A339 A340 A341 A342 A343 A344 A345 A346 A347 A348
A349 A350 A351 A352 A353 A354 A355 A356 A357 A358 A359 A360
A361 A362 A363 A364 A365 A366 A367 A368 A369 A370 A371
A382 A383 A384
A385 A386 A387 A388 A389 A390 A391 A392 A393 A394 A395 A396
A397 A398 A399 A400 A401 A402 A403 A404 A405 A406 A407 A408
A409 A410 A411 A412 A413 A414 A415 A416 A417 A418 A419 A420
A421 A422 A423 A424 A425 A426 A427 A428 A429 A430 A431 A432
A433 A434 A435 A436 A437 A438 A439 A440 A441 A442 A443 A444
A445 A446 A447 A448 A449 A450 A451 A452 A453 A454 A455 A456
A457 A458 A459 A460 A461 A462
A473 A474 A475 A476 A477 A478 A479 A480
A481 A482 A483 A484 A485 A486 A487 A488 A489 A490 A491 A492
A493 A494 A495 A496 A497 A498 A499 A500 A501 A502 A503 A504
A505 A506 A507 A508 A509 A510 A511 A512 A513 A514 A515 A516
A517 A518 A519 A520 A521 A522 A523 A524 A525 A526 A527 A528 B3 B3 B3 B3 B3 B3 B3 B3 B3 B3 B3 B3
A529 A530 A531 A532 A533 A534 A535 A536 A537 A538 A539 A540
A541 A542 A543 A544 A545 - - - - - - -
A564
A565 A566 A567 A568 A569 A570 A571 A572 A573 A574 A575 A576
A577 A578 A579 A580 A581 A582 A583 A584 A585 A586 A587 A588
A589 A590 A591 A592 A593 A594 A595 A596 A597 A598 A599 A600
A601 A602 A603 A604 A605 A606 A607 A608 A609 A610 A611 A612
A613 A614 A615 A616 A617 A618 A619 A620 A621 A622 A623 A624
A625 A626 A627 A628 A629 A630 A631 A632 A633 A634 A635 A636
A654 A655 A656 A657 A658 A659 A660
A661 A662 A663 A664 A665 A666 A667 A668 A669 A670 A671 A672
A685 A686 A687 A688 A689 A690 A691 A692 A693 A694 A695 A696
A697 A698 A699 A700 A701 A702 A703 A704 A705 A706 A707 A708
A709 A710 A711 A712 A713 A714 A715 A716 A717 A718 A719 A720
A721 A722 A723 A724 A725 A726
A733 A744
A745 A746 A747 A748 A749 A750 A751 A752 A753 A754 A755 A756
A757 A758 A759 A760 A761 A762 A763 A764 A765 A766 A767 A768
A769 A770 A771 A772 A773 A774 A775 A776 A777 A778 A779 A780
A781 A782 A783 A784 A785 A786 A787 A788 A789 A790 A791 A792
A793 A794 A795 A796 A797 A798 A799 A800 A801 A802 A803 A804
A805 A806 A807 A808 A809 A810 A811 A812 A813 A814 A815 A816
A817 A828
A829 A830 A831 A832 - - - . : . - - Table 5: Compounds of formula I, represented as compounds of formula
A-Q
wherein Q is Q2, and Q2 is the radical C5:
C5 C5 C5 C5 C5 C5 C5 C5 C5 C5 C5 C5
A1 A2 A3 A4 A5 A6 A7 A8 A9 A10 A11 A12
A13 A14 A15 A16 A17 A18 A19 A20 A21 A22 A23 A24
A25 A26 A27 A28 A29 A30 A31 A32 A33 A34 A35 A36
A37 A38 A39 A40 A41 A42 A43 A44 A45 A46 A47 A48
A49 A50 A51 A52 A53 A54 A55 A56 A57 A58 A59 A60
A61 A62 A63 A64 A65 A66 A67 A68 A69 A70 A71 A72
A73 A74 A75 A76 A77 A78 A79 A80 A81 A82 A83 A84
A85 A86 A87 A88 A89 A90 A91 A92 A93 A94 A95 A96
A97 A98 A99 A100 A101 A102 A103 A104 A105 A106 A107 A108
A109 A110 A111 A112 A113 A114 A115 A116 A117 A118 A119 A120
A121 A122 A123 A124 A125 A126 A127 A128 A129 A130 A131 A132
A133 A134 A135 A136 A137 A138 A139 A140 A141 A142 A143 A144
A145 A146 A147 A148 A149 A150 A151 A152 A153 A154 A155 A156
A157 A158 A159 A160 A161 A162 A163 A164 A165 A166 A167 A168
A169 A170 A171 A172 A173 A174 A175 A176 A177 A178 A179 A180
A181 A182 A183 A184 A185 A186 A187 A188 A189 A190 A191 A192
A193 A194 A195 A196 A197 A198 A199 A200 A201 A202 A203 A204
A205 A206 A207 A208 A209 A210 A211 A212 A213 A214 A215 A216
A217 A218 A219 A220 A221 A222 A223 A224 A225 A226 A227 A228
A229 A230 A231 A232 A233 A234 A235 A236 A237 A238 A239 A240
A241 A242 A243 A244 A245 A246 A247 A248 A249 A250 A251 A252
A253 A254 A255 A256 A257 A258 A259 A260 A261 A262 A263 A264
A265 A266 A267 A268 A269 A270 A271 A272 A273 A274 A275 A276
A277 A278 A279 A280 A281 A282 A283 A284 A285 A286 A287 A288
A289 A290 A291 A292 A293 A294 A295 A296 A297 A298 A299 A300 C5 C5 C5 C5 C5 C5 C5 C C5 C5 C5 C5
A301 A302 A303 A304 A305 A306 A307 A308 A309 A310 A311 A312
A313 A314 A315 A316 A317 A318 A319 A320 A321 A322 A323 A324
A325 A326 A327 A328 A329 A330 A331 A332 A333 A334 A335 A336
A337 A338 A339 A340 A341 A342 A343 A344 A345 A346 A347 A348
A349 A350 A351 A352 A353 A354 A355 A356 A357 A358 A359 A360
A361 A362 A363 A364 A365 A366 A367 A368 A369 A370 A371 A372
A373 A374 A375 A376 A377 A378 A379 A380 A381 A382 A383 A384
A385 A386 A387 A388 A389 A390 A391 A392 A393 A394 A395 A396
A397 A398 A399 A400 A401 A402 A403 A404 A405 A406 A407 A408
A409 A410 A411 A412 A413 A414 A415 A416 A417 A418 A419 A420
A421 A422 A423 A424 A425 A426 A427 A428 A429 A430 A431 A432
A433 A434 A435 A436 A437 A438 A439 A440 A441 A442 A443 A444
A445 A446 A447 A448 A449 A450 A451 A452 A453 A454 A455 A456
A457 A458 A459 A460 A461 A462 A463 A464 A465 A466 A467 A468
A469 A470 A471 A472 A473 A474 A475 A476 A477 A478 A479 A480
A481 A482 A483 A484 A485 A486 A487 A488 A489 A490 A491 A492
A493 A494 A495 A496 A497 A498 A499 A500 A501 A502 A503 A504
A505 A506 A507 A508 A509 A510 A511 A512 A513 A514 A515 A516
A517 A518 A519 A520 A521 A522 A523 A524 A525 A526 A527 A528
A529 A530 A531 A532 A533 A534 A535 A536 A537 A538 A539 A540
A541 A542 A543 A544 A545 A546 A547 A548 A549 A550 A551 A552
A553 A554 A555 A556 A557 A558 A559 A560 A561 A562 A563 A564
A565 A566 A567 A568 A569 A570 A571 A572 A573 A574 A575 A576
A577 A578 A579 A580 A581 A582 A583 A584 A585 A586 A587 A588
A589 A590 A591 A592 A593 A594 A595 A596 A597 A598 A599 A600
A601 A602 A603 A604 A605 A606 A607 A608 A609 A610 A611 A612
A613 A614 A615 A616 A617 A618 A619 A620 A621 A622 A623 A624
A625 A626 A627 A628 A629 A630 A631 A632 A633 A634 A635 A636
A637 A638 A639 A640 A641 A642 A643 A644 A645 A646 A647 A648
A649 A650 A651 A652 A653 A654 A655 A656 A657 A658 A659 A660
A661 A662 A663 A664 A665 A666 A667 A668 A669 A670 A671 A672
A673 A674 A675 A676 A677 A678 A679 A680 A681 A682 A683 A684
A685 A686 A687 A688 A689 A690 A691 A692 A693 A694 A695 A696 C5 C^ C5 C5 C5 C5 C5 C5 C5 C5 C5 C5
A697 A698 A699 A700 A701 A702 A703 A704 A705 A706 A707 A708
A709 A710 A711 A712 A713 A714 A715 A716 A717 A718 A719 A720
A721 A722 A723 A724 A725 A726 A727 A728 A729 A730 A731 A732
A733 A734 A735 A736 A737 A738 A739 A740 A741 A742 A743 A744
A745 A746 A747 A748 A749 A750 A751 A752 A753 A754 A755 A756
A757 A758 A759 A760 A761 A762 A763 A764 A765 A766 A767 A768
A769 A770 A771 A772 A773 A774 A775 A776 A777 A778 A779 A780
A781 A782 A783 A784 A785 A786 A787 A788 A789 A790 A791 A792
A793 A794 A795 A796 A797 A798 A799 A800 A801 A802 A803 A804
A805 A806 A807 A808 A809 A810 A811 A812 A813 A814 A815 A816
A817 A818 A819 A820 A821 A822 A823 A824 A825 A826 A827 A828
A829 A830 A831 A832 - - - - - - - -
Table 6: Compounds of formula I, represented as compounds of formula
A-Q
wherein Q is Q2, and Q2 is the radical C2:
C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 C2
A1 A2 A3 A4 A5 A6 A7 A8 A9 A10 A11 A12
A13 A14 A15 A16 A17 A18 A19 A20 A21 A22 A23 A24
A25 A26 A27 A28 A29 A30 A31 A32 A33 A34 A35 A36
A37 A38 A39 A40 A41 A42 A43 A44 A45 A46 A47 A48
A49 A50 A51 A52 A53 A54 A55 A56 A57 A58 A59 A60
A61 A62 A63 A64 A65 A66 A67 A68 A69 A70 A71 A72
A73 A74 A75 A76 A77 A78 A79 A80 A81 A82 A83 A84
A85 A86 A87 A88 A89 A90 A91 A92 A93 A94 A95 A96
A97 A98 A99 A100 A101 A102 A103 A104 A105 A106 A107 A108
A109 A110 A111 A112 A113 A114 A115 A116 A117 A118 A119 A120
A121 A122 A123 A124 A125 A126 A127 A128 A129 A130 A131 A132 C2 C2 C2 C^ ^ C2 C2 C2 C2 C2 C2 C2
A133 A134 A135 A136 A137 A138 A139 A140 A141 A142 A143 A144
A145 A146 A147 A148 A149 A150 A151 A152 A153 A154 A155 A156
A157 A158 A159 A160 A161 A162 A163 A164 A165 A166 A167 A168
A169 A170 A171 A172 A173 A174 A175 A176 A177 A178 A179 A180
A181 A182 A183 A184 A185 A186 A187 A188 A189 A190 A191 A192
A193 A194 A195 A196 A197 A198 A199 A200 A201 A202 A203 A204
A205 A206 A207 A208 A209 A210 A211 A212 A213 A214 A215 A216
A217 A218 A219 A220 A221 A222 A223 A224 A225 A226 A227 A228
A229 A230 A231 A232 A233 A234 A235 A236 A237 A238 A239 A240
A241 A242 A243 A244 A245 A246 A247 A248 A249 A250 A251 A252
A253 A254 A255 A256 A257 A258 A259 A260 A261 A262 A263 A264
A265 A266 A267 A268 A269 A270 A271 A272 A273 A274 A275 A276
A277 A278 A279 A280 A281 A282 A283 A284 A285 A286 A287 A288
A289 A290 A291 A292 A293 A294 A295 A296 A297 A298 A299 A300
A301 A302 A303 A304 A305 A306 A307 A308 A309 A310 A311 A312
A313 A314 A315 A316 A317 A318 A319 A320 A321 A322 A323 A324
A325 A326 A327 A328 A329 A330 A331 A332 A333 A334 A335 A336
A337 A338 A339 A340 A341 A342 A343 A344 A345 A346 A347 A348
A349 A350 A351 A352 A353 A354 A355 A356 A357 A358 A359 A360
A361 A362 A363 A364 A365 A366 A367 A368 A369 A370 A371 A372
A373 A374 A375 A376 A377 A378 A379 A380 A381 A382 A383 A384
A385 A386 A387 A388 A389 A390 A391 A392 A393 A394 A395 A396
A397 A398 A399 A400 A401 A402 A403 A404 A405 A406 A407 A408
A409 A410 A411 A412 A413 A414 A415 A416 A417 A418 A419 A420
A421 A422 A423 A424 A425 A426 A427 A428 A429 A430 A431 A432
A433 A434 A435 A436 A437 A438 A439 A440 A441 A442 A443 A444
A445 A446 A447 A448 A449 A450 A451 A452 A453 A454 A455 A456
A457 A458 A459 A460 A461 A462 A463 A464 A465 A466 A467 A468
A469 A470 A471 A472 A473 A474 A475 A476 A477 A478 A479 A480
A481 A482 A483 A484 A485 A486 A487 A488 A489 A490 A491 A492
A493 A494 A495 A496 A497 A498 A499 A500 A501 A502 A503 A504
A505 A506 A507 A508 A509 A510 A511 A512 A513 A514 A515 A516
A517 A518 A519 A520 A521 A522 A523 A524 A525 A526 A527 A528 C2 C2 C^ C2 ^ C2 C2 C2 C2 C2 C2 C2
A529 A530 A531 A532 A533 A534 A535 A536 A537 A538 A539 A540
A541 A542 A543 A544 A545 A546 A547 A548 A549 A550 A551 A552
A553 A554 A555 A556 A557 A558 A559 A560 A561 A562 A563 A564
A565 A566 A567 A568 A569 A570 A571 A572 A573 A574 A575 A576
A577 A578 A579 A580 A581 A582 A583 A584 A585 A586 A587 A588
A589 A590 A591 A592 A593 A594 A595 A596 A597 A598 A599 A600
A601 A602 A603 A604 A605 A606 A607 A608 A609 A610 A611 A612
A613 A614 A615 A616 A617 A618 A619 A620 A621 A622 A623 A624
A625 A626 A627 A628 A629 A630 A631 A632 A633 A634 A635 A636
A637 A638 A639 A640 A641 A642 A643 A644 A645 A646 A647 A648
A649 A650 A651 A652 A653 A654 A655 A656 A657 A658 A659 A660
A661 A662 A663 A664 A665 A666 A667 A668 A669 A670 A671 A672
A673 A674 A675 A676 A677 A678 A679 A680 A681 A682 A683 A684
A685 A686 A687 A688 A689 A690 A691 A692 A693 A694 A695 A696
A697 A698 A699 A700 A701 A702 A703 A704 A705 A706 A707 A708
A709 A710 A711 A712 A713 A714 A715 A716 A717 A718 A719 A720
A721 A722 A723 A724 A725 A726 A727 A728 A729 A730 A731 A732
A733 A734 A735 A736 A737 A738 A739 A740 A741 A742 A743 A744
A745 A746 A747 A748 A749 A750 A751 A752 A753 A754 A755 A756
A757 A758 A759 A760 A761 A762 A763 A764 A765 A766 A767 A768
A769 A770 A771 A772 A773 A774 A775 A776 A777 A778 A779 A780
A781 A782 A783 A784 A785 A786 A787 A788 A789 A790 A791 A792
A793 A794 A795 A796 A797 A798 A799 A800 A801 A802 A803 A804
A805 A806 A807 A808 A809 A810 A811 A812 A813 A814 A815 A816
A817 A818 A819 A820 A821 A822 A823 A824 A825 A826 A827 A828
A829 A830 A831 A832 Table 7: Compounds of formula I. represented as compounds of formula
A-Q
wherein A is A10:
A10 A10 A10 A10 A10 A10 A10 A10 A10 A10 A10 A10
C1 - C3 C4 - C6 C7 C8 C9 C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 C21 C22 C23 C24 C25 C26 C27 - - -
Table 8: Compounds of formula I. represented as compounds of formula
A-Q
wherein A is A556:
A556 A556 A556 A556 A556 A556 A556 A556 A556 A556 A556 A556
C1 - C3 C4 - C6 C7 C8 C9 C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 C21 C22 C23 C24 C25 C26 C27
Table 8: Compounds of formula I. represented as compounds of formula
A-Q
wherein A is A646:
A646 A646 A646 A646 A646 A646 A646 A646 A646 A646 A646 A646 A646 A646 A646 A646 A646 A646 A646 A646 A646 A646 A646 A646
C1 - C3 C4 - C6 C7 C8 C9 C10 C11 C12
C13 C14 C15 C16 C17 C18 C19 C20 C21 C22 C23 C24
C25 C26 C27 _ - - - - - -
Compounds of formulae 2.1 and 2.3 to 2.13. c are known by the names imazamox, imazethapyr, imazaquin, imazapyr, dimethenamid, atrazine, terbuthylazine, simazine, terbutryn, cyanazine, ametryn, terbumeton, prohexadione calcium, sethoxydim, clethodim, tepraloxydim, flumetsulam, metosulam, pyridate, bromoxynil, ioxynil, sulcotrione, carfentrazone, sulfentrazone, isoxaflutole, glufosinate, primisulfuron, prosulfuron, rimsulfuron, halosulfuron, nicosulfuron, ethoxysulfuron, flazasulfuron, triasulfuron, tralkoxydim, chlorsulfuron and thifensulfuron-methyl and are described in the Pesticide Manual, eleventh ed., British Crop Protection Council, 1997 under the entry numbers 412, 415, 414, 413, 240, 34, 692, 651 , 693, 168, 20, 691 , 595, 648, 146, 49, 339, 495, 626, 88, 425, 664, 112, 665, 436, 382, 589, 613, 644, 389, 519, 287, 325, 723, 717, 139 and 704. The compound of formula 2.13 wherein Y2, Y3 and Y4 are methine, Yi is C-l, R74 is COOMe, Y5 is nitrogen, Y6 is methyl and Y7 is methoxy is known by the name iodosulfuron (especially the sodium salt) from AGROW No. 296, 16th January 1998, page 22. The compound of formula 2.13 wherein Yi, Y2, Y3 and Y4 are methine, R74 is trifluoromethyl, Y5 is nitrogen, Y6 is trifluoromethyl and Y7 is methoxy is known by the name tritosulfuron and is described in DE-A-40 38 430. The compound of formula 2.13 wherein Y2 is NH-CHO, Yi, Y3 and Y4 are methine, R7 is CONMe2, Y5 is methine and Y6 and Y are methoxy is known by the name foramsulfuron and is described, for example, in WO 95/29899.
The compound of formula 2.13 wherein Y2 is C-CH2-NH-SO2CH3, Yi, Y3 and Y4 are methine, R7 is COOMe, Y5 is methine, and Y6 and Y7 are methoxy, is known by the name mesosulfuron and is described, for example, under Chemical Abstracts Registry Number 208465-21-8.
Dichlorprop is described under Chemical Abstracts Registry Number 15165-67-0.
The S enantiomer of the compound of formula 2.12 is registered under the CAS-Reg. No. [35597-44-5]. The compound of the general formula 2.2, aRS,1'S(-)N-(1 '-methyl-2'-methoxy- ethyl)-N-chloroacetyl-2-ethyl-6-methylaniline, and a compound of the general formula 2.3, (1 S,aRS)-2-chloro-N-(2,4-dimethyl-3-thienyl)-N-(2-methoxy-1 -methylethyl)-acetamide, are described, for example, in WO 97/34485. The compound of formula 2.9 wherein R69 is NO2 is known by the name mesotrione and is described, for example, in US-A-5 006 158. The compound of formula 2.6 wherein R62 is ethoxy, R63 is fluorine, Y is methine, R64 is methoxycarbonyl, R6s is hydrogen and R66 is chlorine is known by the name cloransulam, for example from AGROW No. 261 , 2nd August 1996, page 21. The compound of formula 2.6 wherein R62 is methoxy, R63 is hydrogen, Y is C-F, R64 is fluorine, R65 is hydrogen and R66 is fluorine is known by the name florasulam and is described in US-A-5 163 995.
The following compounds of the composition according to the invention are described in the Pesticide Manual, eleventh ed., British Crop Protection Council, 1997:
Compound of formula and/or name Pesticide Manual eleventh ed., Entry No
2.14 (metribuzin) 497
2.15 (aclonifen) 8
2.16 (glyphosate) 383
2.17 (bentazone) 65
2.18 (pendimethalin) 557
2.19 (dicamba) 210
2.20 (butylate) 100
2.22 (clomazone) 150
2.23 (2,4-D) 192
2.24 (flumiclorac) 340
2.25 (fluthiacet-methyl) 359
2.26 (flurtamone) 356
2.27 (flumioxazin) 341
2.28 (paraquat) 550
2.29 (azafenidin) 37
2.30 (fluthiamide) 51
2.33 (sulfosate) 383
2.34 (asulam) 33
2.35 (norflurazon) 526
2.36 (terbacil) 689 Compound of formula and/or name Pesticide Manual eleventh ed., Entry No.:
2.37 (thiazopyr) 702
2.38 (dithiopyr) 259
2.39 (hexazinone) 400
2.40 (diuron) 260
2.41 (MCPA) 455
2.42 (mecoprop) 459
2.43 (tebuthiuron) 683 prosulfocarb 612 pyraflufen-ethyl 617 fenoxaprop-P-ethyl 309 diclofop-methyl 219 amidosulfuron 21 flupyrsulfuron 348 flupyrsulfuron-methyl-sodium 348 metsulfuron-methyl 498 sulfosulfuron 668 tribenuron-methyl 728 imazamethabenz-methyl 411 chlorotoluron 134 isoproturon 433 methabenzthiazuron 477 bifenox 69 fluoroglycofen-ethyl 344 imazosulfuron 416 diflufenican 232 bilanafos 71 ethalfluralin 279 trifluralin 740 fluthiamid 51 isoxaben 435 triallate 722
2,4-DB 199
MCPB 457 Compound of formula and/or name Pesticide Manual eleventh ed., Entry No clopyralid 153 fluroxypyr 354 quinmerac 636 benazolin-ethyl 55 difenzoquat 229 dithiopyr 259 quinclorac 635 prodiamine 593 benefin 57
The following compounds of the composition according to the invention are described in the Pesticide Manual, 12th ed., British Crop Protection Council, 2000:
The compound of formula 2.7 wherein R6 is hydrogen and its preparation are described in US-A-3 790 571 ; the compound of formula 2.6 wherein R62 is ethoxy, Z is nitrogen, R63 is fluorine, R64 is chlorine and R65 is hydrogen and R66 is chlorine is described in US-A-5 498 773.
The compound of formula 2.21 and its preparation are described in US-A-5 183 492; the compound of formula 2.22 is described, under the name isoxachlortole, in AGROW No. 296, 16th January 1998, page 22. The compound of formula 2.31 is described, under the name f entrazamide, in The 1997 British Crop Protection Conference - Weeds, Conference Proceedings Vol. 1 , 2-8, pages 67 to 72; the compound of formula 2.32 is described, under the name JV 485 (isoxapropazol), in The 1997 British Crop Protection Conference - Weeds, Conference Proceedings Vol. 1 , 3A-2, pages 93 to 98. The compound of formula 2.44 is known by the name pethoxamid and is described, for example, in EP-A-0 206 251. The compound of formula 2.45 is known by the name procarbazone and is described, for example, in EP-A-0 507 171 ; the compound of formula 2.46 is known by the name fluazolate and is described, for example, in US-A-5 530 126. The compound of formula 2.47 is known by the name cinidon-ethyl and is described, for example, in DE-A-40 37 840. The compound of formula 2.48 is known by the name benzfendizone and is described, for example, in WO 97/08953. The compound of formula 2.49 is known as diflufenzopyr and is described, for example, in EP-A-0 646 315. The compound of formula 2.50 (amicarbazone) and its preparation are disclosed in DD 298 393 and in US-A-5 194 085. The compound of formula 2.51 (flufenpyr-ethyl) is described in Abstracts of Papers American Chemical Society, (2000) Vol. 220, No. Part 1 , pp. AGRO 174. The compounds of formula 2.52 are described in WO 01/17352; the compound of formula 2.53 is described in US-A-4 881 966.
It is extremely surprising that the combination of the compound of formula I with one or more active ingredients selected from formulae 2.1 to 2.53 and the compounds prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amido- sulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlorotoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, trifluralin, fluthiamide, isoxaben, triallate, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin exceeds the additive effect on the weeds to be controlled that is to be expected in principle and thus broadens the range of action of the individual active ingredients especially in two respects: firstly, the rates of application of the individual compounds of formulae I and 2.1 to 2.53 and the compounds prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl- sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlorotoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, trifluralin, fluthiamide, isoxaben, triallate, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin are reduced while a good level of action is maintained and, secondly, the composition according to the invention achieves a high level of weed control also in those cases where the individual substances, in the low rates of application range, have become useless from the agronomic standpoint. The result is a considerable broadening of the spectrum of weeds and an additional increase in selectivity in respect of the crops of useful plants, as is necessary and desirable in the event of an unintentional overdose of active ingredient. The composition according to the invention, while retaining excellent control of weeds in crops of useful plants, also allows greater flexibility in succeeding crops.
The composition according to the invention can be used against a large number of agronomically important weeds, such as Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Phaseolus, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica. The composition according to the invention is suitable for all methods of application conventionally used in agriculture, e.g. pre-emergence application, post-emergence application and seed dressing. The composition according to the invention is suitable especially for controlling weeds in crops of useful plants, such as cereals, rape, sugar beet, sugar cane, plantation crops, rice, maize and soybeans, and also for non-selective weed control.
"Crops" are to be understood to mean also those crops which have been made tolerant to herbicides or classes of herbicides (le.g. HPPD-inhibitors, ALS-inhibitors, EPSPS-(5-enol- pyruvyl-shikimate-3-phosphate-synthease)inhibitors or GS- (glutamine-synthease)inhibitors) as a result of conventional methods of breeding or genetic engineering. Examples for crops which have been made tolerant to imidazolinone as a result of conventional methods of breeding (mutagenese) is Clearfiled® canola. An example for crops which have been made tolerant to herbicides or classes of herbicides as a result of genetic engineering are maize seeds which are resistant to glyphosate and glufosinate respectively, commercially available under the brand Roundup Ready® and Liberty Link®.
The composition according to the invention comprises the compound of formula I and the compounds of formulae 2.1 to 2.53 and prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlorotoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, trifluralin, fluthiamide, isoxaben, triallate, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin in any mixing ratio, but usually has an excess of one component over the others. Generally, the mixing ratios (ratios by weight) of the compound of formula I and the mixing partners of formulae 2.1 to 2.53 and prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop- methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlorotoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, trifluralin, fluthiamide, isoxaben, triallate, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin are from 1 :2000 to 2000:1 , especially from 200:1 to 1 :200.
The rate of application may vary within wide limits and depends on the nature of the soil, the method of application (pre- or post-emergence; seed dressing; application to the seed furrow; no tillage application etc.), the crop plant, the weed to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop. The active ingredient mixture according to the invention can generally be applied at a rate of from 1 to 5000 g of active ingredient mixture/ha.
The mixtures of the compound of formula I with the compounds of formulae 2.1 to 2.53 and the compounds prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron- methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlorotoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, trifluralin, fluthiamide, isoxaben, triallate, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin may be used in unmodified form, that is to say as obtained in the synthesis. Preferably, however, they are formulated in customary manner, together with the adjuvants conventionally used in formulation technology, such as solvents, solid carriers or surfactants, for example into emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, wetting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances. The formulations, i.e. the compositions, preparations or mixtures comprising the compounds of formulae I and 2.1 to 2.53 and prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl- sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlorotoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, trifluralin, fluthiamide, isoxaben, triallate, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin and also, where appropriate, one or more solid or liquid formulation adjuvants, are prepared in a manner known per se, e.g. by intimately mixing and/or grinding the active ingredients with the formulation adjuvants, e.g. solvents or solid carriers. In addition, surface-active compounds (surfactants) may also be used in the preparation of the formulations.
Examples of solvents and solid carriers are given, for example, in WO 97/34485, page 6.
Depending on the nature of the compound of formula I to be formulated, suitable surface- active compounds are non-ionic, cationic and/or anionic surfactants and surfactant mixtures having good emulsifying, dispersing and wetting properties.
Examples of suitable anionic, non-ionic and cationic surfactants are listed, for example, in WO 97/34485, pages 7 and 8.
Also suitable in the preparation of the herbicidal compositions according to the invention are the surfactants conventionally used in formulation technology, which are described, inter alia, in "McCutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood New Jersey, 1981 , Stache, H., "Tensid-Taschenbuch", Carl Hanser Verlag, Munich/Vienna, 1981 and M. and J. Ash, "Encyclopedia of Surfactants", Vol l-lll, Chemical Publishing Co., New York, 1980-81.
The compositions according to the invention may additionally comprise an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of such oils or mixtures of such oils and oil derivatives. In the composition according to the invention, the amounts of oil additive employed are generally from 0.01 to 2 %, based on the spray mixture. The oil additive can, for example, be added to the spray tank in the desired concentration after the spray mixture has been prepared.
Preferred oil additives comprise mineral oils or an oil of vegetable origin such as, for example, rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, such as AMIGO® obtainable from Rhόne-Poulenc Canada Inc., alkyl esters of oils of vegetable origin such as, for example, the methyl derivatives, or an oil of animal origin such as fish oil or beef tallow. Especially preferred is the "additive type A", which contains as active components essentially 80 % by weight of alkyl esters of fish oils and 15 % by weight of methylated rapeseed oil, and also 5 % by weight of customary emulsifiers and pH modifiers.
Especially preferred oil additives comprise alkyl esters of higher fatty acids (C8-C22), especially the methyl derivatives of Cι2-Cι8 fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid. Those esters are known as methyl laurate (CAS-111-82-0), methyl palmitate (CAS-112-39-0) and methyl oleate (CAS-112-62-9). A preferred fatty acid methyl ester derivative is Emery® 2230 and 2231 (Henkel subsidiary company Cognis GmbH, DE).
The application and action of the oil additives can be improved by combining them with surface-active substances such as non-ionic, anionic or cationic surfactants. Examples of suitable anionic, non-ionic and cationic surfactants are listed in WO 97/34485 on pages 7 and 8.
Preferred surface-active substances are anionic surfactants of the dodecylbenzylsulfonate type, especially the calcium salts thereof, and also non-ionic surfactants of the fatty alcohol ethoxylate type. Special preference is given to ethoxylated Cι2-C22 fatty alcohols having a degree of ethoxylation of from 5 to 40. Examples of commercially available preferred surfactants are the Genapol types (Clariant AG, Muttenz, Switzerland). The concentration of the surface-active substances based on the total additive is generally from 1 to 30 % by weight. Surface-active substances the use of which is likewise preferred are silicone surfactants, especially polyalkyl-oxide-modified heptamethyltrisiloxanes, such as are obtainable commercially as, for example, Silwet L-77®, and also perfluorinated surfactants.
Examples of oil additives consisting of mixtures of oils or mineral oils or derivatives thereof with surfactants are Edenor ME SU®, Turbocharge® (Zeneca Agro, Stoney Creek, Ontario, CA) or, more especially, Actipron® (BP Oil UK Limited, GB).
The addition of an organic solvent to the oil additive/surfactant mixture can, furthermore, bring about a further increase in action. Suitable solvents are, for example, Solvesso® (ESSO) or Aromatic Solvent® (Exxon Corporation) types. The concentration of those solvents can be from 10 to 80 % of the total weight.
Such oil additives, which are also described, for example, in US-A-4 834 908, are especially preferred for the composition according to the invention. An especially preferred oil additive is known under the name MERGE®, it can be obtained from the BASF Corporation and a basic description thereof is given, for example, in US-A-4 834 908 in col. 5, as Example COC-1. A further oil additive that is preferred according to the invention is SCORE® (Novartis Crop Protection Canada).
In addition to the above-listed oil additives, formulations of alkylpyrrolidones such as are marketed commercially, for example as Agrimax®, may additionally be added to the spray mixture in order to enhance the action of the compositions according to the invention. There may likewise be used, for the purpose of enhancing action, formulations of synthetic latices, for example polyacrylamide, polyvinyl compounds or poly-1-p-menthene, such as are available on the market as, for example, Bond®, Courier® or Emerald®. In addition, propionic acid-containing solutions, such as Eurogkem Pen-e-trate®, may be added to the spray mixture as action-enhancing agents.
To the compositions according to the invention comprising the compounds of formulae 2.52 there are preferably added one or more of the above-listed oil additives or of the above-listed alkylpyrrolidone formulations, synthetic latices or propionic acid-containing solutions. The herbicidal formulations usually contain from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of active ingredient mixture comprising a compound of formula I together with the compounds of formulae 2.1 to 2.53 and the compounds prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron- methyl, imazamethabenz-methyl, flucarbazone, chlorotoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, trifluralin, fluthiamide, isoxaben, triallate, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin, from 1 to 99.9 % by weight of a solid or liquid formulation adjuvant, and from 0 to 25 % by weight, especially from 0.1 to 25 % by weight, of a surfactant.
Whereas commercial products are usually formulated as concentrates, the end user will normally employ dilute formulations. The compositions may also comprise further ingredients, such as stabilisers, e.g. vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soybean oil), antifoams, e.g. silicone oil, preservatives, viscosity regulators, binders, tackifiers, and also fertilisers or other active ingredients. Preferred formulations have especially the following compositions: (% = percent by weight)
Emulsifiable concentrates: active ingredient mixture: 1 to 90 %, preferably 5 to 20 % surfactant: 1 to 30 %, preferably 10 to 20 % liquid carrier: 5 to 94 %, preferably 70 to 85 %
Dusts: active ingredient mixture: 0.1 to 10 %, preferably 0.1 to 5 % solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %
Suspension concentrates: active ingredient mixture: 5 to 75 %, preferably 10 to 50 % water: 94 to 24 %, preferably 88 to 30 % surfactant: 1 to 40 %, preferably 2 to 30 % Wettable powders: active ingredient mixture: 0.5 to 90 %, preferably 1 to 80 % surfactant: 0.5 to 20 %, preferably 1 to 15 % solid carrier: 5 to 95 %, preferably 15 to 90 %
Granules: active ingredient mixture: 0.1 to 30 %, preferably 0.1 to 15 % solid carrier: 99.5 to 70 %, preferably 97 to 85 %
The following Examples illustrate the invention further, but do not limit the invention.
F1. Emulsifiable concentrates a) b) c) d) active ingredient mixture 5 % 10 % 25 % 50 % calcium dodecylbenzenesulfonate 6 % 8 % 6 % 8 % castor oil polyglycol ether 4 % - 4 % 4 %
(36 mol of ethylene oxide) octylphenol polyglycol ether - 4 % - 2 %
(7-8 mol of ethylene oxide) cyclohexanone - - 10 % 20 % o arom. hydrocarbon mixture 85 % 78 % 55 % 16 % o
C9-Cι2
Emulsions of any desired concentration can be obtained from such concentrates by dilution with water.
F2. Solutions a) b) c) d) active ingredient mixture 5 % 10 % 50 % 90 %
1 -methoxy-3-(3-methoxy- propoxy)-propane - 20 % 20 % - polyethylene glycol MW 400 20 % 10 % - -
N-methyl-2-pyrrolidone - - 30 % 10 % arom. hydrocarbon mixture 75 % 60 % - -
C9-Cι2
The solutions are suitable for use in the form of microdrops. F3. Wettable powders a) b) c) d) active ingredient mixture 5% 25% 50% 80% sodium lignosulfonate 4% - 3% - sodium lauryl sulfate 2% 3% - 4% sodium diisobutylnaphthalene- sulfonate - 6% 5% 6% octylphenol polyglycol ether - 1 % 2% -
(7-8 mol of ethylene oxide) highly dispersed silicic acid 1 % 3% 5% 10% kaolin 88% 62% 35% -
The active ingredient is mixed thoroughly with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of any desired concentration.
F4. Coated granules a) b) c) active ingredient mixture 0.1 % 5% 15% highly dispersed silicic acid 0.9 % 2% 2% inorganic carrier 99.0 % 93% 83%
(diameter 0.1 -1 mm) e.g. CaCO3 or SiO2
The active ingredient is dissolved in methylene chloride and applied to the carrier by spraying, and the solvent is then evaporated off in vacuo.
F5. Coated granules a) b) c) active ingredient mixture 0.1 % 5% 15% polyethylene glycol MW 200 1.0 % 2% 3% highly dispersed silicic acid 0.9 % 1 % 2% inorganic carrier 98.0 % 92% 80%
(diameter 0.1 - 1 mm) e.g. CaCO3 or SiO2
The finely ground active ingredient is uniformly applied, in a mixer, to the carrier moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner. F6. Extruder granules a) b) c) d) active ingredient mixture 0.1 % 3% 5% 15% sodium lignosulfonate 1.5 % 2% 3% 4% carboxymethylcellulose 1.4 % 2% 2% 2% kaolin 97.0 % 93% 90% 79%
The active ingredient is mixed and ground with the adjuvants, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.
F7. Dusts a) b) ) active ingredient mixture 0.1 % 1 % 5% talcum 39.9 % 49% 35% kaolin 60.0 % 50% 60%
Ready-to-use dusts are obtained by mixing the active ingredient with the carriers and grinding the mixture in a suitable mill.
F8. Suspension concentrates a) b) c) d) active ingredient mixture 3% 10% 25% 50% ethylene glycol 5% 5% 5% 5% nonylphenol polyglycol ether - 1 % 2% -
(15 mol of ethylene oxide) sodium lignosulfonate 3% 3% 4% 5% carboxymethylcellulose 1 % 1 % 1 % 1 %
37 % aqueous formaldehyde 0.2 % 0.2 % 0.2 % 0.2 % solution silicone oil emulsion 0.8 % 0.8 % 0.8 % 0.8 % water 87% 79% 62% 38%
The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.
It is often more practical for the compound of formula I and the mixing partner or partners of formulae 2.1 to 2.53 and prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl- sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlorotoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, trifluralin, fluthiamide, isoxaben, triallate, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin to be formulated separately and to be brought together in the desired mixing ratio in the applicator in the form of a "tank mixture" in water shortly before application.
The compositions according to the invention may additionally comprise growth regulators, such as, for example, trinexapac (744), chlormequat chloride (129), clofencet (148), cyclanilide (170), ethephon (281 ), flurprimidol (355), gibberellic acid (379), inabenfide (421), maleic hydrazide (449), mefluidide (463), mepiquat chloride (465), paclobutrazol (548), prohexadione-calcium (595), uniconazole (746) or thidiazuron (703). Fungicides, such as, for example, azoxystrobin (43), epoxiconazole (48), benomyl (60), bromuconazole (89), bitertanol (77), carbendazim (107), cyproconazole (189), cyprodinil (190), diclomezine (220), difenoconazole (228), diniconazole (247), epoxiconazole (48), ethirimol (284), etridiazole (294), fenarimol (300), fenbuconazole (302), fenpiclonil (311), fenpropidin (313), fenpropimorph (314), ferimzone (321 ), fludioxonil (334), fluquinconazole (349), flutolanil (360), flutriafol (361), imazalil (410), ipconazole (426), iprodione (428), isoprothiolane (432), kasugamycin (438), kresoxim-methyl (439), spiroxamine (441 ), mepronil (466), myclobutanil (505), nuarimol (528), pefurazoate (554), pencycuron (556), phthalide (576), probenazole (590), prochloraz (591 ), propiconazole (607), pyrazophos (619), pyroquilon (633), quinoxyfen (638), quintozene (639), tebuconazole (678), tetraconazole (695), thiabendazole (701), thifluzamide (705), triadimefon (720), triadimenol (721 ), tricyclazole (734), tridemorph (736), triflumizole (738), triforine (742), triticonazole (745) or vinclozolin (751 ), may also be present in the compositions according to the invention. The number in parentheses after each active ingredient indicates the entry number of the active ingredient in the Pesticide Manual, eleventh ed., British Crop Protection Council, 1997.
Biological Examples:
A synergistic effect exists whenever the action of the active ingredient combination of the compound of formula I with compounds of formulae 2.1 to 2.53 and prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlorotoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, trifluralin, fluthiamide, isoxaben, triallate, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin is greater than the sum of the actions of the active ingredients applied separately.
The herbicidal action to be expected We for a given combination of two herbicides can be calculated as follows (see COLBY, S.R., "Calculating synergistic and antagonistic response of herbicide combinations", Weeds 15, pages 20-22, 1967:
We = X + [Y • (100 - X) 1100]
wherein:
X = percentage herbicidal action on treatment with the compound of formula I at a rate of application of p kg per hectare, compared with the untreated control (= 0 %).
Y = percentage herbicidal action on treatment with a compound of formula 2.1 to 2.53 and the compounds prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron- methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlorotoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, trifluralin, fluthiamide, isoxaben, triallate, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin at a rate of application of q kg per hectare, compared with the untreated control.
We = expected herbicidal action (percentage herbicidal action compared with the untreated control) following treatment with the compounds of formulae I and 2.1 to 2.53 and the compounds prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron- methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlorotoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, trifluralin, fluthiamide, isoxaben, triallate, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin at a rate of application of p + q kg of active ingredient per hectare.
When the action actually observed is greater than the value to be expected We, there is a synergistic effect.
The synergistic effect of the combinations of a compound of formula I with the compounds of formulae 2.1 to 2.53 and the compounds prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlorotoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, trifluralin, fluthiamide, isoxaben, triallate, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin is demonstrated in the following Examples.
Experiment description - pre-emergence test:
Monocotyledonous and dicotyledonous test plants are sown in standard soil in plastics pots. Directly after sowing, the test compounds are applied in aqueous suspension by spraying (500 litres of water/ha). The rates of application depend on the optimum concentrations determined under field conditions and greenhouse conditions. The test plants are then grown in the greenhouse under optimum conditions. The tests are evaluated after 36 days (% action, 100 % = plant has died, 0 % = no phytotoxic action). The mixtures used in this test exhibit good results.
Experiment description - post-emergence test:
The test plants are grown to the 2- to 3-leaf stage in plastics pots under greenhouse conditions. A standard soil is used as cultivation substrate. At the 2- to 3-leaf stage, the herbicide is applied to the test plants both alone and in admixture. Application is carried out using an aqueous suspension of the test compounds in 500 litres of water/ha. The rates of application depend on the optimum concentrations determined under field conditions and greenhouse conditions. The tests are evaluated after 33 days (% action, 100 % = plant has died, 0 % = no phytotoxic action). In this test, too, the mixtures used exhibit good results.
It has been shown, surprisingly, that specific safeners are suitable for mixing with the synergistic composition according to the invention. The present invention accordingly relates also to a selectively herbicidal composition for controlling grasses and weeds in crops of useful plants, especially in maize crops, that comprises a compound of formula I, one or more compounds selected from the compounds of formulae 2.1 to 2.53 and the compounds prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop- methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlorotoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, trifluralin, fluthiamide, isoxaben, triallate, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin, and a safener (counter agent, antidote) that protects the useful plants, but not the weeds, against the phytotoxic action of the herbicide, as well as to the use of such a composition in the control of weeds in crops of useful plants.
There is accordingly also proposed in accordance with the invention a selectively herbicidal composition that, in addition to comprising customary inert formulation adjuvants, such as carriers, solvents and wetting agents, comprises as active ingredient a mixture of a) an amount, effective for herbicide synergism, of the compound of formula I and one or more compounds selected from the compounds of formulae 2.1 to 2.53 and the compounds prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop- methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlorotoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, trifluralin, fluthiamide, isoxaben, triallate, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin, and b) an amount, effective for herbicide antagonism, of a compound selected from the compound of formula 3.1 and the compound of formula 3.2
and the compound of formula 3.3
thereof and salts and hydrates thereof, and the compound of formula 3.4
and the compound of formula 3.5
and the compound of formula 3.6 and the compound of formula 3.7
and the compound of formula 3.8
and of formula 3.9
CI2CHCON(CH2CH=CH2)2 (3.9),
and of formula 3.10
and of formula 3.11
and of formula 3.12
(3.12) and methyl and ethyl esters thereof and salts thereof,
especially the sodium salt, and of formula 3.13
and of formula 3.14
and of formula 3.15
and of formula 3.16
and of formula 3.17
The invention relates also to a selectively herbicidal composition that, in addition to comprising customary inert formulation adjuvants, such as carriers, solvents and wetting agents, comprises as active ingredient a mixture of a) a herbicidally effective amount of the compound of formula I and b) an amount, effective for herbicide antagonism, of a compound selected from the compounds of formulae 3.1 , 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 3.10, 3.1 1 , 3.12, 3.13, 3.14, 3.15, 3.16 and 3.17.
Preferred compositions according to the invention comprise as safener a compound selected from the compounds of formulae 3.1 , 3.3 and 3.8. Such safeners are suitable especially for the compositions according to the invention that comprise the above-mentioned preferred compounds of formulae 2.1 to 2.53 or prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlorotoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, trifluralin, fluthiamide, isoxaben, triallate, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin.
Preferred compositions according to the invention also comprise an amount, effective for herbicide antagonism, of 2-(5-chloroquinolin-8-yloxy)acetic acid -1 -methyl hexyl ester of formula 3.3, or a hydrate thereof, especially 1 -methylhexyl-(5-chloroquinolin-8-yloxy)acetate tetrahydrate, the free acid thereof or a salt thereof of formula
wherein M is a mono-, di- or tri-valent metal, ammonium, N(R)4 or HN(R)3, wherein the substituents R are identical to or different from one another and are d-Cι6alkyl or CrCι6hydroxyalkyl, or M is S(Ra)3 or P(Ra)4, wherein the substituents Ra are identical to or different from one another and are Cι-C20alkyl, C2-C20alkenyl, C2-C20alkynyl, aryl substituted by CrC20alkyl, C2-C20alkenyl or by C2-C20alkynyl, or heteroaryl substituted by G|-C20alkyl, C2-C20alkenyl or by C2-C20alkynyl, or 2 substituents Ra together with the sulfur or phosphorus atom to which they are bonded form a 5- or 6-membered ring.
The metal atoms M that may be present in formula 3.3a are preferably those of alkali metals or alkaline earth metals, especially sodium, potassium, calcium, magnesium and also especially aluminium and iron as preferred examples of trivalent metals. Of the alkyl and hydroxyalkyl substituents R, preference is given to those having from 12 to 16 carbon atoms and also to those having from 1 to 4 carbon atoms. The groups N(R)4 and HN(R)3 especially contain one long-chain and 2 or 3 short-chain alkyl groups, such as, for example, hexadecyl-triethylammonium, tetradecyl-triethylammonium, dodecyl-triethyl- ammonium, dodecyl-ethyl-dimethylammonium and also tetradodecylammonium. Preferred alkyl groups Ra contain from 1 to 12, especially from 1 to 6, carbon atoms. The alkyl groups R and Ra may themselves be substituted, for example by halogen, alkoxy or haloalkoxy, each of which preferably has from 1 to 4 carbon atoms. Preferred alkenyl and alkynyl groups Ra contain from 2 to 12 carbon atoms. They may contain more than one unsaturated bond and may be substituted by halogen, alkoxy or haloalkoxy, each of which preferably has from 1 to 4 carbon atoms. Suitable examples of aryl groups Ra are phenyl, naphthyl, tetrahydro- naphthyl, indanyl and indenyl, phenyl being preferred. Such groups may be substituted by the above-mentioned alkyl, alkenyl and alkynyl groups. There may be mentioned as heteroaryl groups Ra preferably 5- and 6-membered rings that contain especially nitrogen and/or oxygen atoms, such as, for example, pyridyl, pyrimidinyl, triazinyl, thienyl, thiazolyl, pyrazolyl, imidazolyl, piperidyl, dioxolanyl, morpholinyl and tetrahydrofuryl. Such heterocycles too may themselves be substituted by the above-mentioned alkyl, alkenyl and alkynyl groups. Groups of two Ra substituents may, together with the sulfur or phosphorus atom to which they are bonded, form a ring. Preferably, 5- or 6-membered, saturated rings are formed. The sulfonium and phosphonium cations that can be used according to the invention are described, for example, in WO 00/44227.
Preferred salts of 2-(5-chloroquinolin-8-yloxy)acetic acid -1 -methyl hexyl ester comprise a compound of formula 3.3a wherein M is sodium, potassium or tri(hydroxyethylene)ammonium.
A further group of preferred salts of 2-(5-chloroquinolin-8-yloxy)acetic acid -1 -methyl hexyl ester comprises those wherein, in formula 3.3a, M is calcium, magnesium, aluminium, iron, trimethylsulfonium, triphenylsulfonium, tetraphenylphosphonium, triphenyl-methyl- phosphonium, triphenyl-benzylphosphonium, C12-C16alkyl-trimethyIammonium, C12-Cι6alkyl- triethylammonium, tetradodecylammonium or dodecyl-ethyl-dimethylammonium.
The salts of formula 3.3a can be prepared according to customary methods, for example by reaction of 2-(5-chloroquinolin-8-yloxy)acetic acid -1 -methyl hexyl ester with an equimolar amount of a metal hydroxide in alcoholic solution at room temperature.
The salts listed in the following Table are obtainable in that manner:
Table A: Compounds of formula 3.3a:
Further preferred compositions according to the invention comprise a compound of formula 2.53 and an amount, effective for herbicide antagonism, of 2-(5-chloroquinolin-8-yloxy)-1- methylhexyl ester of formula 3.3, or a hydrate thereof, especially 1 -methylhexyl (5-chloroquinolin-8-yloxy)acetate tetrahydrate, the free acid thereof or a salt thereof of formula 3.3a.
Combinations of the compound of formula I with the compound of formula 3.1 have proved to be especially effective compositions. Such a composition is used preferably together with the compound of formula 2.2a (2.2a, aRS,1,S(-)N-(1'-methyl-2'-methoxyethyl)-N-
chloroacetyl-2-ethyl-6-methylaniline).
The invention relates also to a method for the selective control of weeds in crops of useful plants, which comprises treating the useful plants, seeds or cuttings thereof, or the area of cultivation thereof, with a herbicidally effective amount of the herbicide of formula I, optionally one or more herbicides selected from the compounds of formulae 2.1 to 2.53 and the compounds prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron- methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlorotoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, trifluralin, fluthiamide, isoxaben, triallate, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin, and an amount, effective for herbicide antagonism, of a safener from formulae 3.1 to 3.17.
The compounds of formulae 3.1 to 3.17 are known and are described, for example, in the Pesticide Manual, eleventh ed., British Crop Protection Council, 1997 under the entry numbers 61 (formula 3.1 , benoxacor), 304 (formula 3.2, fenclorim), 154 (formula 3.3, cloquintocet), 462 (formula 3.4, mefenpyr-diethyl), 377 (formula 3.5, furilazole), 363 (formula 3.8, fluxofenim), 213 (formula 3.9, dichlormid) and 350 (formula 3.10, flurazole). The compound of formula 3.11 is known as MON 4660 (Monsanto) and is described, for example, in EP-A-0 436 483. The compound of formula 3.17 is described, for example, in US-A-6 162 762.
The compound of formula 3.6 (AC 304415) is described, for example, in EP-A-0 613 618, and the compound of formula 3.7 in DE-A-29 48 535. The compounds of formula 3.12 are described in DE-A-43 31 448, and the compound of formula 3.13 in DE-A-3525 205. The compound of formula 3.14 is known, for example, from US-A-5 215 570, and the compound of formula 3.15 from EP-A-0 929 543. The compound of formula 3.17 is described in WO 99/00020. In addition to the compound of formula 3.17, the other 3-(5-tetrazolyl- carbonyl)-2-quinolones described in WO 99/00020, especially the compounds specifically disclosed in Tables 1 and 2 on pages 21 to 29, are also suitable for protecting crop plants against the phytotoxic action of the compounds of formula I.
As crop plants that can be protected by the safeners of formulae 3.1 to 3.17 against the damaging effect of the above-mentioned herbicides there come into consideration especially cereals, cotton, soybeans, sugar beet, sugar cane, plantation crops, rape, maize and rice, more especially maize. "Crops" are to be understood to mean also those crops which have been made tolerant to herbicides or classes of herbicides as a result of conventional methods of breeding or genetic engineering.
The weeds to be controlled may be both monocotyledonous and dicotyledonous weeds, such as, for example Stellaria, Agrostis, Digitaria, Avena, Apera, Brachiaria, Phalaris, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoria, Sagittaria, Panicum, Bromus, Alopecurus, Sorghum halepense, Sorghum bicolor, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica.
Areas of cultivation include the areas of ground on which the crop plants are already growing or which have been sown with the seeds of those crop plants, as well as ground intended for the cultivation of such crop plants.
Depending on the intended use, a safener of formula 3.1 to 3.17 can be used in the pretreatment of the seed of the crop plant (dressing of the seeds or cuttings) or can be introduced into the soil before or after sowing. It can, however, also be applied, either alone or together with the herbicide, after emergence of the plants. The treatment of the plants or seeds with the safener can therefore in principle be carried out independently of the time at which the herbicide is applied. The plants can, however, also be treated by simultaneous application of herbicide and safener (e.g. in the form of a tank mixture). The ratio of the rate of application of safener to the rate of application of herbicide depends largely on the method of application. In the case of field treatment, which is carried out either using a tank mixture comprising a combination of safener and herbicide or by separate application of safener and herbicide, the ratio of herbicides to safener is generally from 100:1 to 1 :10, preferably from 20:1 to 1 :1. In the case of field treatment it is usual to apply from 0.001 to 1.0 kg of safener/ha, preferably from 0.001 to 0.25 kg of safener/ha.
The rate of application of herbicides is generally from 0.001 to 5 kg/ha, but preferably from 0.005 to 0.5 kg/ha.
The compositions according to the invention are suitable for all methods of application conventionally used in agriculture, e.g. pre-emergence application, post-emergence application and seed dressing.
In the case of seed dressing, generally from 0.001 to 10 g of safener/kg of seed, preferably from 0.05 to 2 g of safener/kg of seed, are applied. When the safener is applied in liquid form shortly before sowing, with soaking of the seeds, then advantageously the safener solutions used contain the active ingredient in a concentration of from 1 to 10 000 ppm, preferably from 100 to 1000 ppm.
For the purpose of application, the safeners of formulae 3.1 to 3.17 or combinations of those safeners with a herbicide of formula I and optionally one or more herbicides selected from formulae 2.1 to 2.53 and the compounds prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlorotoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, trifluralin, fluthiamide, isoxaben, triallate, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin are advantageously formulated together with adjuvants customary in formulation technology, e.g. into emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules.
Such formulations are described, for example, in WO 97/34485, pages 9 to 13. The formulations are prepared in known manner, e.g. by intimately mixing and/or grinding the active ingredients with liquid or solid formulation adjuvants, e.g. solvents or solid carriers. In addition, surface-active compounds (surfactants) can also be used in the preparation of the formulations. Solvents and solid carriers suitable for that purpose are mentioned, for example, in WO 97/34485, page 6.
Depending on the nature of the compound of formulae I, 2.1 to 2.53 and the compounds prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop- methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlorotoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, trifluralin, fluthiamide, isoxaben, triallate, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin and 3.1 to 3.17 to be formulated, there come into consideration as surface-active compounds non- ionic, cationic and/or anionic surfactants and surfactant mixtures having good emulsifying, dispersing and wetting properties. Examples of suitable anionic, non-ionic and cationic surfactants are listed, for example, on pages 7 and 8 of WO 97/34485. Also suitable for the preparation of the herbicidal compositions according to the invention are the surfactants conventionally employed in formulation technology, which are described, inter alia, in "McCutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood New Jersey, 1981 , Stache, H., "Tensid-Taschenbuch", Carl Hanser Verlag, Munich/Vienna, 1981 and M. and J. Ash, "Encyclopedia of Surfactants", Vol. I-III, Chemical Publishing Co., New York, 1980-81.
The herbicidal formulations usually contain from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of active ingredient mixture comprising the compound of formula I, a compound selected from the compounds of formulae 2.1 to 2.53 and the compounds prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop- methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlorotoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, trifluralin, fluthiamide, isoxaben, triallate, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin and the compounds of formulae 3.1 to 3.17, from 1 to 99.9 % by weight of a solid or liquid formulation adjuvant and from 0 to 25 % by weight, especially from 0.1 to 25 % by weight, of a surfactant. Whereas commercial products are usually formulated as concentrates, the end user will normally employ dilute formulations.
The compositions may also comprise further ingredients, such as stabilisers, e.g. vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soybean oil), anti- foams, e.g. silicone oil, preservatives, viscosity regulators, binders, tackifiers, and also fertilisers or other active ingredients. For the use of safeners of formulae 3.1 to 3.17, or of compositions comprising them, in the protection of crop plants against the damaging effects of herbicides of formulae I and 2.1 to 2.53 and the compounds prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron- methyl, imazamethabenz-methyl, flucarbazone, chlorotoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, trifluralin, fluthiamide, isoxaben, triallate, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin, various methods and techniques come into consideration, such as, for example, the following:
i) Seed dressing a) Dressing of the seeds with a wettable powder formulation of a compound from formulae 3.1 to 3.17 by shaking in a vessel until uniformly distributed over the seed surface (dry dressing). In that procedure approximately from 1 to 500 g of compound from formulae 3.1 to 3.17 (4 g to 2 kg of wettable powder) are used per 100 kg of seed. b) Dressing of the seeds with an emulsifiable concentrate of a compound from formulae 3.1 to 3.17 according to method a) (wet dressing). c) Dressing by immersing the seeds for from 1 to 72 hours in a liquor comprising from 100 to 1000 ppm of a compound from formulae 3.1 to 3.17 and optionally subsequently drying the seeds (immersion dressing).
Dressing the seed or treating the germinated seedling are naturally the preferred methods of application, because treatment with the active ingredients is directed entirely at the target crop. Generally from 1 to 1000 g of antidote, preferably from 5 to 250 g of antidote, are used per 100 kg of seed, but depending on the methodology, which also allows other active ingredients or micronutrients to be added, concentrations above or below the limits indicated may be employed (repeat dressing).
ii) Application as a tank mixture
A liquid formulation of a mixture of antidote and herbicide is used (ratio by weight of the one to the other from 10:1 to 1 :100), the rate of application of herbicide being from 0.005 to
5.0 kg per hectare. Such tank mixtures are applied before or after sowing. iii) Application to the seed furrow
The compound from formulae 3.1 to 3.17 is introduced into the open, sown seed furrow in the form of an emulsifiable concentrate, wettable powder or granules. Once the seed furrow has been covered over, the herbicide is applied in the usual manner pre-emergence. iv) Controlled release of active ingredient
The compound from formulae 3.1 to 3.17 is applied in solution to mineral carrier granules or polymerised granules (urea/formaldehyde) and dried. If desired, it is also possible to apply a coating that allows the active ingredient to be released in metered amounts over a specific period of time (coated granules).
Preferred formulations have especially the following compositions:
(% = percent by weight)
Emulsifiable concentrates: active ingredient mixture: 1 to 90 %, preferably 5 to 20 % surfactant: 1 to 30 %, preferably 10 to 20 % liquid carrier: 5 to 94 %, preferably 70 to 85 %
Dusts: active ingredient mixture: 0.1 to 10 %, preferably 0.1 to 5 % solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %
Suspension concentrates: active ingredient mixture: 5 to 75 %>, preferably 10 to 50 % water: 94 to 24 %, preferably 88 to 30 % ,. surfactant: 1 to 40 %, preferably 2 to 30 % Wettable powders: active ingredient mixture: 0.5 to 90 %, preferably 1 to 80 % surfactant: 0.5 to 20 %, preferably 1 to 15 % solid carrier: 5 to 95 %, preferably 15 to 90 %
Granules: active ingredient mixture: 0.1 to 30 %, preferably 0.1 to 15 % solid carrier: 99.5 to 70 %, preferably 97 to 85 %
The following Examples illustrate the invention further, but do not limit the invention.
Formulation Examples for mixtures of herbicides of formula I, optionally of formulae 2.1 to 2.53 and the compounds prosulfocarb. picolinafen. pyraflufen-ethyl, beflubutamid. fenoxaprop-P-ethyl. diclofop-methyl, amidosulfuron. flupyrsulfuron. flupyrsulfuron-methyl- sodium, metsulfuron-methyl. sulfosulfuron. tribenuron-methyl. imazamethabenz-methyl. flucarbazone, chlorotoluron. isoproturon. methabenzthiazuron, bifenox, fluoroglycofen-ethyl. imazosulfuron, diflufenican, bilanafos. ethalfluralin. trifluralin, fluthiamide. isoxaben. triallate. 2,4-DB, dichlorprop. MCPA. MCPB, mecoprop, MCPP. mecoprop-P, clopyralid. fluroxypyr. guinmerac. benazolin-ethyl. difenzoquat. cyhalofop-butyl, dithiopyr, guinclorac. prodiamine. benefin and trifluralin and safeners of formulae 3.1 to 3.17 (% = percent by weight)
F1. Emulsifiable concentrates a) b) c) d) active ingredient mixture 5 % 10 % 25 % 50 % calcium dodecylbenzenesulfonate 6 % 8 % 6 % 8 % castor oil polyglycol ether 4 % - 4 % 4 %
(36 mol of ethylene oxide) octylphenol polyglycol ether - 4 % - 2 %
(7-8 mol of ethylene oxide) cyclohexanone - - 10 % 20 % o arom. hydrocarbon mixture 85 % 78 % 55 % 16 % Ό
Emulsions of any desired concentration can be obtained from such concentrates by dilution with water. F2. Solutions a) b) c) d) active ingredient mixture 5% 10% 50% 90%
1 -methoxy-3-(3-methoxy- propoxy)-propane - 20% 20% - polyethylene glycol MW 400 20% 10% - _
N-methyl-2-pyrrolidone - - 30 % 10 % arom. hydrocarbon mixture .75 % 60 %
C9-Cι2
The solutions are suitable for use in the form of microdrops.
F3. Wettable powders a) b) c) d) active ingredient mixture 5% 25% 50% 80% sodium lignosulfonate 4% - 3% - sodium lauryl sulfate 2% 3% - 4% sodium diisobutylnaphthalene- sulfonate - 6% 5% 6% octylphenol polyglycol ether - 1 % 2% -
(7-8 mol of ethylene oxide) highly dispersed silicic acid 1 % 3% 5% 10% kaolin 88% 62% 35% _
The active ingredient is mixed thoroughly with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of any desired concentration.
F4. Coated granules a) b) c) active ingredient mixture 0.1 % 5% 15% highly dispersed silicic acid 0.9 % 2% 2% inorganic carrier 99.0 % 93% 83%
(diameter 0.1 - 1 mm) e.g. CaCO3 or SiO2
The active ingredient is dissolved in methylene chloride and applied to the carrier by spraying, and the solvent is then evaporated off in vacuo. F5. Coated granules a) b) c) active ingredient mixture 0.1 % 5% 15% polyethylene glycol MW 200 1.0 % 2% 3% highly dispersed silicic acid 0.9 % 1 % 2% inorganic carrier 98.0 % 92% 80%
(diameter 0.1 - 1 mm) e.g. CaCO3 or SiO2
The finely ground active ingredient is uniformly applied, in a mixer, to the carrier moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.
F6. Extruder granules a) b) c) d) active ingredient mixture 0.1 % 3% 5% 15% sodium lignosulfonate 1.5 % 2% 3% 4% carboxymethylcellulose 1.4 % 2% 2% 2% kaolin 97.0 % 93% 90% 79%
The active ingredient is mixed and ground with the adjuvants, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.
F7. Dusts a) b) c) active ingredient mixture 0.1 % 1 % 5% talcum 39.9 % 49% 35% kaolin 60.0 % 50% 60%.
Ready-to-use dusts are obtained by mixing the active ingredient with the carriers and grinding the mixture in a suitable mill.
F8. Suspension concentrates a) b) c) d) active ingredient mixture 3% 10% 25% 50% ethylene glycol 5% 5% 5% 5% nonylphenol polyglycol ether - 1 % 2% - (15 mol of ethylene oxide) sodium lignosulfonate 3% 3% 4% 5% carboxymethylcellulose 1 % 1 % 1 % 1 % 37 % aqueous formaldehyde 0.2 % 0.2 % 0.2 % 0.2 % solution silicone oil emulsion 0.8 % 0.8 % 0.8 % 0.8 % water 87 % 79 % 62 % 38 %
The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.
It is often more practical for the compounds of formulae I, 2.1 to 2.53 and the compounds prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop- methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlorotoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, trifluralin, fluthiamide, isoxaben, triallate, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin and 3.1 to 3.17 to be formulated separately and then to be brought together in the desired mixing ratio in the applicator in the form of a "tank mixture" in water shortly before application.
The ability of the safeners of formulae 3.1 to 3.17 to protect crop plants against the phytotoxic action of herbicides of formula I is illustrated in the following Examples.
Biological Example: Safening action
The test plants are grown in plastics pots under greenhouse conditions to the 4-leaf stage. At that stage, either the herbicides alone or the mixtures of the herbicides with the test compounds being tested as safeners are applied to the test plants. The test compounds are applied in the form of an aqueous suspension prepared from a 25 % wettable powder (Example F3, b)), using 500 litres of water/ha. 4 weeks after application, the phytotoxic action of the herbicides on the crop plants, e.g. maize and cereals, is evaluated using a percentage scale. 100 % indicates that the test plant has died, 0 % indicates no phytotoxic action. The mixtures according to the invention exhibit a good action in this test.

Claims

What is claimed is:
1. A selectively herbicidal composition that, in addition to comprising customary inert formulation adjuvants, comprises as active ingredient a mixture of a) a herbicidally effective amount of the compound of formula I
wherein p is 0 or 1 ;
Ri is a Ci-Cealkylene, C3-C6alkenylene or C3-C6alkynylene chain, which may be substituted one or more times by halogen or by R5, the unsaturated bonds of the chain not being attached directly to the substituent Xi;
Xi is oxygen, -O(CO)-, -(CO)O-, -O(CO)O-, -N(R6)-O-, -O-NR51-, thio, sulfinyl, sulfonyl, -SO2NR7-, -NR52SO2- or -NR8-;
R2 is a Cι-C8alkyl, C3-C6alkenyl or C3-C6alkynyl group, which is substituted one or more times by halogen, hydroxy, amino, formyl, nitro, cyano, mercapto, carbamoyl, C Cealkoxy, CrCealkoxycarbonyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, C3-C6- cycloalkyl, halo-substituted C3-C6cycloalkyl, C3-C6alkenyloxy, C3-C6alkynyloxy, CrCehaloalkoxy, C3-C6haloalkenyloxy, cyano-CrC6alkoxy, CrC6alkoxy-CrC6alkoxy, CrC6alkoxy- CrCealkoxy-CrCealkoxy, CrC6alkylthio-CrC6alkoxy, Cι-C6alkylsulfinyl-Cι-C6alkoxy, C C6- alkylsulfonyl-Cι-C6alkoxy, Ci-Cealkoxycarbonyl-Ci-Cealkoxy, CrC6alkoxycarbonyl, CrC6- alkylcarbonyl, CrC6alkylthio, Cι-C6alkylsulfinyl, Cι-C6alkylsulfonyl, Cι-C6haloalkylthio, Cι-C6haloalkylsulfinyl, CrC6haloalkylsulfonyl, oxiranyl (which may in turn be substituted by CrC6aikyl), (3-oxetanyl)-oxy (which may in turn be substituted by Cι-C6alkyl), benzylthio, benzylsulfinyl, benzylsulfonyl, Cι-C6alkylamino, di(CrC6alkyl)amino, R9S(O)2O, RioN(Rn)SO2-, rhodano, phenyl, phenoxy, phenylthio, phenylsulfinyl or by phenylsulfonyl; wherein the phenyl- or benzyl-containing groups may in turn be substituted by one or more C C6alkyl, CrCehaloalkyl, Cι-C6alkoxy, CrCehaloalkoxy, halogen, cyano, hydroxy or nitro groups, or
R2 is phenyl, which may be substituted one or more times by CrCealkyl, CrCehaloalkyl, CrC6alkoxy, CrCehaloalkoxy, halogen, cyano, hydroxy or by nitro; or R2 is C3-C6cycloalkyl; C3-C6cycloalkyl substituted by Cι-C6alkoxy or by Cι-C6alkyl; 3-oxetanyl or 3-oxetanyl substituted by CrC6alkyl; or, when Q is Q2 or Q3, or when Q is Qi wherein Rι4 and R22 denote a C2-C3alkylene chain, R2 may additionally be a five- to ten-membered, monocyclic or fused bicyclic ring system, which may be aromatic, saturated or partially saturated and which may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur, the ring system being bonded to the substituent Xi directly or via a CrC4alkylene, C2-C4alkenyl-CrC4alkylene, C2-C4alkynyl- Ci-C4alkylene, -N(R12)-Cι-C4alkylene, -SO-Cι-C4alkylene or -SO2-Cι-C4alkylene group, and wherein each ring system may contain no more than two oxygen atoms and no more than two sulfur atoms and the ring system may itself be mono-, di- or tri-substituted by Cι-C6alkyl, CrCehaloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, Cι-C6alkoxy, hydroxy, CrCehaloalkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, mercapto, Cι-C6alkylthio, Ci-Cehaloalkylthio, C3-C6alkenylthio, C3-C6haloalkenylthio, C3-C6alkynylthio, C2- C5alkoxyalkylthio, C3-C5acetylalkylthio, C3-C6alkoxycarbonylalkylthio, C2-C cyanoalkylthio, Cι-C6alkylsulfinyl, CrC6haloalkylsulfinyl, Cι-C6alkylsulfonyl, d-Cehaloalkylsulfonyl, aminosulfonyl, Cι-C2alkylaminosulfonyl, di(d-C2alkyl)aminosulfonyl, di(Ci-C4alkyl)amino, halogen, cyano, nitro, phenyl or by benzylthio, wherein phenyl and benzylthio may in turn be substituted on the phenyl ring by d-C3alkyl, d-C3haloalkyl, d-C3alkoxy, C C3haloalkoxy, halogen, cyano or by nitro, and wherein the substituents on the nitrogen in the heterocyclic ring are other than halogen; or R2 is hydrogen or unsubstituted d-C8alkyl, when either a) Ri is substituted by the group R5, or b) Q is the group Q2, or c) Q is the group Q3 when Xi is -O(CO)-, -(CO)O-, -N(R6)-O-, -O-NR5 , -SO2NR7-, -NR52SO2- or -NR8-; or d) Q is the group Qi when Xi is -N(R6)-O-, -O-NR51-, -SO2NR7-, -NR52SO2- or -NR8-, or e) Q is the group Qi wherein R14 and R22 in Qi denote a C2-C3alkylene chain and Xi is -O(CO)- or -(CO)O-;
R3 is Cι-C3haloalkyl;
R4 is hydrogen, halogen, Cι-C3alkyl, C C3haloalkyl, d-C3alkoxy, Cι-C3alkoxy-Cι-C3alkyl or
C C3alkoxy-CrC3alkoxy;
R5 is hydroxy, d-C6alkoxy, C3-C6cycloalkyloxy, CrC6alkoxy-CrC8alkoxy, d-C6alkoxy-
Ci-Cβalkoxy-CrCealkoxy or C C2alkylsulfonyloxy; Rβ, R7, Rs, Rg> R10. R11, R12, R51 and R52 are each independently of the others hydrogen, d-Cealkyl, CrC6haloalkyI, Cι-C6alkoxycarbonyl, Cι-C6alkylcarbonyl, Cι-Cealkoxy-Cι-C6alkyl, Ci-Cβalkoxy-Ci-CealkyI substituted by Cι-C6alkoxy, benzyl, or phenyl, wherein phenyl and benzyl may in turn be substituted one or more times by Cι-C6alkyl, CrCehaloalkyl, d-C6- alkoxy, CrC6haloalkoxy, halogen, cyano, hydroxy or by nitro; wherein R6 is not hydrogen when R9 is hydrogen, d-C6alkoxycarbonyl or d-C6alkylcarbonyl; Q is Qi
wherein
Ai is C(Rι4R15), NR16 or oxygen;
A2 is C(Rι7Rι8), C(O), -C=N-O-Rι9, oxygen, thio, sulfinyl, sulfonyl, -NR20 or ethylene; with the provisos that Ai is other than oxygen when A2 is oxygen, C(O), thio, sulfinyl, -C=N-O-R19,
NR20 or C(R17Rι8), R17 and R18 being each independently of the other Cι-C4alkoxy, d-C4- alkylthio, CrC4alkylsulfinyl or d-C4alkylsulfonyl; and that Ai is other than NRι6 when A2 is thio, sulfinyl or C(Rι7Rι8), R17 and Rι8 being each independently of the other d-C4alkoxy,
Cι-C alkylthio, Cι-C alkylsulfinyl or Cι-C alkylsulfonyl;
R14 and R22 are each independently of the other hydrogen, d-C alkyl, C C haloalkyl, C3-C4- alkenyl, C3-C4alkynyl, d-C4alkylthio, d-C4alkylsulfinyl, Cι-C4alkylsulfonyl, d-C4alkylsulfonyl- oxy, Cι-C4alkoxy, Cι-C4alkoxycarbonyl or Cι-C4alkylcarbonyl;
R15 and R21 are each independently of the other hydrogen, Cι-C4alkyl, Cι-C haloalkyl, C3-C4- alkenyl or C3-C4alkynyl;
Rι7 is hydrogen, d-C4alkyl, Cι-C4haloalkyl, d-C4alkoxy, Cι-C4alkylthio, Ci -C4alkylsulf inyl or
Cι-C alkylsulfonyl;
R18 is hydrogen, d-C4alkyl, C C haloalkyl, C3-C alkenyl, C3-C4alkynyl, Ci-C4alkoxy, Cι-C - alkylthio, CrC4alkylsulfinyl, d-C4alkylsulfonyl or di(C C4)alkoxyalkyl-Cι-C4alkyl;
R20 is Cι-C4alkyl, C3-C6cycloalkyl, C3-C4alkenyl, C3-C4alkynyl, d-C4alkylcarbonyl, d-C4alkyl- carbonyloxy, di(Cι-C4)alkylaminocarbonyl or benzyl, wherein the phenyl group may be substituted one or more times by d-C6alkyl, d-C6haloalkyl, d-C6alkoxy, CrCehaloalkoxy, halogen, cyano, hydroxy or by nitro;
R19 and R16 are each independently of the other hydrogen, d-C alkyl, C3-C6cycloalkyl,
C3-C4alkenyl, C3-C alkynyl, benzyl or phenyl, wherein phenyl and benzyl may in turn be substituted one or more times by d-C6alkyl, CrC6haloalkyl, Ci-Cealkoxy, d-C6haloalkoxy, halogen, cyano, hydroxy or by nitro; or R14 and R22 together form a C2-C3alkylene chain; or R14 and R15 together and/or R17 and Rι8 together and/or R21 and R^ together form a
C2-C4alkylene chain, which may be interrupted by oxygen and/or by carbonyl and/or by sulfur, with the proviso that the oxygen and sulfur atoms are separated by at least one methylene group; or R14 and Rι8 together form a C2-C4alkylene chain; or
R22 and R18 together form a C2-C4alkylene chain; or R 8 forms, together with R22 or Rι4, a direct bond; or R16 and Rι8 together form a C2-C4alkylene chain;
R13 is hydroxy; O"M+ wherein M+ is an alkali metal cation or an ammonium cation; halogen,
Cι-Cι2alkylsulfonyloxy, amino, Cι-C4alkylthio, Cι-Cι2alkylsulfinyl, Cι-Cι2alkylsulfonyl, d-Cι2- haloalkylthio, Cι-Cι2haloalkylsulfinyl, d-Cι2haloalkylsulfonyl, Cι-C6alkoxy-CrCealkylthio,
CrC6alkoxy-Cι-C6alkylsulfinyI, Cι-Cealkoxy-Ci-C6alkylsulfonyl, C3-Cι2alkenylthio, C3-d2- alkenylsulfinyl, C3-Cι2alkenylsulfonyl, C3-C12alkynylthio, C3-Cι2alkynylsulfinyl, C3-C12alkynyl- sulfonyl, CrC4alkoxycarbonyl-Cι-C4alkylthio, Cι-C4alkoxycarbonyl-Cι-C4alkylsulfinyl, Cι-C4- alkoxycarbonyl-d-C4alkylsulfonyl, (d-C4alkoxy)2P(O)O, Cι-C4alkyl-(d-C4alkoxy)P(O)O,
H(d-C4alkoxy)P(O)O, R23R24N, R25R26NNH, R27R28NC(O)O-, R29R30NC(O)NH-, d-C18alkyl- carbonyloxy, C2-C18alkenylcarbonyloxy, C2-Cι8alkynylcarbonyloxy, C3-C6cycloalkylcarbonyl- oxy, Ci-Cι2alkoxycarbonyloxy, Ci-C12alkylthiocarbonyloxy or C C12alkylthiocarbamoyl, wherein the alkyl, alkenyl and alkynyl groups may be substituted by halogen, CrC6alkoxy,
CrC6alkylthio, d-C6alkylsulfinyl, CrC6alkylsulfonyl or by cyano; or R13 is phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, phenylsulfonylamino, phenyl- sulfonyloxy or benzoyloxy, wherein the phenyl groups may in turn be substituted by one or more halogen, nitro, cyano, Cι-C4alkyl, Cι-C4haloalkyl, C C4alkoxy or d-C4haloalkoxy groups; or R13 is a group Hetrthio, Het2-sulfinyl, Het3-sulfonyl, Het4-(CO)O or Het5-N(R33); wherein
Heti, Het2, Het3, Het4 and Het5 are each independently of the others a five- to ten- membered, monocyclic or fused bicyclic ring system, which may be aromatic or partially saturated and which may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur and wherein each ring system may contain no more than two oxygen atoms and no more than two sulfur atoms and the ring system may itself be substituted by d-C6alkyl,
Cι-C6haloalkyl, d-C6alkoxy, Cι-C6haloalkoxy, Cι-C6alkylthio, d-C6alkylsulfinyl, d-
C6alkylsulfonyl, di(d-C alkyl)aminosuIfonyl, di(Cι-C alkyl)amino, halogen, cyano, nitro or by phenyl, and wherein the substituents on the nitrogen in the heterocyclic ring are other than halogen;
R23, R24» R25, R26, R27, R28, R29, R30 and R33 are each independently of the others hydrogen or d-Cealkyl; or R23 and R24 together or R25 and R26 together or R27 and R28 together or R29 and R30 together are pyrrolidino, piperidino, morpholino or thiomorpholino, each of which may be mono- or poly-substituted by methyl groups; or Q is Q2
wherein
R3 is hydrogen, CrC4alkyl, d-C4haloalkyl, C3-C6cycloalkyl, C2-C4alkenyl, C2-C4alkynyl or benzyl, wherein the phenyl group may be substituted one or more times by d-C6alkyl, CrC6haloalkyl, Cι-C6alkoxy, Cι-C6haloalkoxy, halogen, cyano, hydroxy or by nitro; R35 is hydrogen, d-C4alkyl, d-C4haloalkyl, C3-C6cycloalkyl, C3-C4alkenyl, C3-C4alkynyl or benzyl, wherein the phenyl group may be substituted one or more times by CrC6alkyl, d-Cehaloalkyl, d-C8alkoxy, d-C6haloalkoxy, halogen, cyano, hydroxy or by nitro; R36 is hydroxy; O"M+ wherein M+ is an alkali metal cation or an ammonium cation; halogen, Cι-C12alkylsulfonyloxy, amino, Cι-C4alkylthio, d-Cι2alkylsulfinyl, Cι-C12alkylsulfonyl, Cι-C12haloalkylthio, Cι-C12haloalkylsulfinyl, d-C12haloalkylsulfonyl, CrC6alkoxy-Cι-C6alkyl- thio, Cι-C6alkoxy-CrC6alkylsulfinyl, CrCealkoxy-Ci-Cealkylsulfonyl, C3-Cι2alkenylthio, C3-C12alkenylsulfinyl, C3-Cι2alkenylsulfonyl, C3-Cι2alkynylthio, C3-C12alkynylsulfinyl, C3-C12alkynylsulfonyl, CrC4alkoxycarbonyl-C C4alkylthio, d-C4alkoxycarbonyl-Ci-C4alkyl- sulfinyl, d-C4alkoxycarbonyl-Cι-C4alkylsulfonyl, (Ci-C4alkoxy)2P(O)O, C C4alkyl- (Ci-C4alkoxy)P(O)O, H(Cι-C4alkoxy)P(O)O, R37R38N, R39R40NNH, R41R42NC(O)O-, R 3R NC(O)NH-, Cι-Cι8alkylcarbonyloxy, C2-C18alkenylcarbonyloxy, C2-C18alkynylcarbonyl- oxy, C3-C6cycloalkylcarbonyloxy, Cι-Cι2alkoxycarbonyloxy, d-Cι2alkylthiocarbonyloxy or Cι-Cι2alkylthiocarbamoyl, wherein the alkyl, alkenyl and alkynyl groups may be substituted by halogen, d-C6alkoxy, d-C6alkylthio, Cι-C6alkylsulfinyl, Cι-C6alkylsulfonyl or by cyano; or R36 is phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, phenylsulfonylamino, phenyl- sulfonyloxy or benzoyloxy, wherein the phenyl groups may in turn be substituted one or more times by halogen, nitro, cyano, Cι-C4alkyl, d-C4haloalkyl, d-C4alkoxy or by C C4halo- alkoxy, or R36 is a group Het7-thio, Het8-sulfinyl, Het9-sulfonyl, Hetι0-(CO)O or Hetn-N(R47); wherein Het7, Het8, Het9, Hetι0 and Hetn are each independently of the others a five- to ten- membered, monocyclic or fused bicyclic ring system, which may be aromatic or partially saturated and which may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur and wherein each ring system may contain no more than two oxygen atoms and no more than two sulfur atoms and the ring system may itself be substituted by CrC6alkyl, d-Cehaloalkyl, d-C6alkoxy, CrCehaloalkoxy, CrC6alkyIthio, CrC6aIkylsulfinyl, Ci-Cealkylsulfonyl, di(CrC4alkyI)aminosulfonyl, di(Cι-C4alkyl)amino, halogen, cyano, nitro or by phenyl, and wherein the substituents on the nitrogen in the heterocyclic ring are other than halogen; R37. R38. R39. R4o, R41, R42, R43, R4 and R47 are each independently of the others hydrogen or Cι-C6alkyl; or
R37 and R38 together or R39 and R40 together or R4ι and R42 together or R43 and R^ together are pyrrolidino, piperidino, morpholino or thiomorpholino, each of which may be mono- or poly-substituted by methyl groups; or Q is Q3
wherein
R49 is Cι-C4alkyl, Cι-C4haloalkyl, C3-C6cycloalkyl or halo-substituted C3-C6cycloalkyl; R50 is Ci-C3alkylene, which may be substituted by halogen, hydroxy, Cι-C6alkoxy, C2-C6- alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, Ci-Cealkoxy-d-Cealkoxy, CrC6alkoxy-CrC6alkoxy- Cι-C6alkoxy, (3-oxetanyl)-oxy, or by (3-oxetanyl)-oxy substituted by Cι-C6alkyl, or by benzylthio, benzylsulfinyl, benzylsulfonyl, phenyl, phenoxy, phenylthio, phenylsulfinyl or by phenylsulfonyl, wherein the phenyl- and benzyl-containing groups may in turn be substituted by one or more d-C6alkyl, CrC6haloalkyl, CrC6alkoxy, d-C6haloalkoxy, halogen, cyano, hydroxy or nitro groups; or R50 is phenyl, wherein the phenyl-containing group may in turn be substituted by one or more CrC6alkyl, CrCehaloalkyl, Cι-C6alkoxy, d-Cehaloalkoxy, halogen, cyano, hydroxy or nitro substituents, or R50 is C3-C6cycloalkyl, C3-C8cycloalkyl substituted by d-C6alkoxy or by Cι-C6alkyl, 3- oxetanyl or 3-oxetanyl substituted by d-C6alkyl; and n is 0, 1 or 2; or an agronomically acceptable salt/N-oxide/isomer/enantiomer of such a compound except for the compound 4-hydroxy-3-[2-(2-methoxyethoxyethoxymethyl)-6- trifluoromethylpyridine-3-carbonyl]-bicyclo[3.2.1]oct-3-en-2-one, and with the provisos that
-R XrR2 is other than CrC alkoxy-CrC alkoxy-d-C4alkyl when a) Q is Qi wherein Ai is C(R14R15) and A2 is C(Rι7Rι8), Rι5, Rι7 and Rι8 are hydrogen and Rι4 and R22 together form a C2-C3alkylene chain; and when b) Q is Qi, Rι4 and R22 do not together form a C2-C3alkylene chain, Ai is C(R 4R15), or Ai is NR16 and A2 is oxygen; and when c) Q is Q3, and b) a synergistically effective amount of one or more compounds selected from a compound of formula 2.1
wherein R5ι is CH2-OMe, ethyl or hydrogen;
R52 is hydrogen, or R5ι and R52 together are the group -CH=CH-CH=CH-; and a compound of formula 2.2
wherein R53 is ethyl, R54 is methyl or ethyl, and R55 is -CH(Me)-CH2OMe, <S>-CH(Me)-CH2OMe, CH2OMe or CH2O-CH2CH3; and a compound of formula 2.3
wherein R56 is CH(Me)-CH2OMe or <S>CH(Me)-CH2OMe; and a compound of formula 2.4
wherein R57 is chlorine, methoxy or methylthio, R58 is ethyl or isopropyl, and R59 is ethyl, isopropyl, -C(CN)(CH3)-CH3 or tert-butyl; and a compound of formula 2.5
wherein R60 is ethyl or n-propyl, R6ι is COO" 1/2 Ca++, -CH2-CH(Me)S-CH2CH3, the group
and X is oxygen, N-O-CH2CH3 or
N-O-CH2CH=CH-CI; and a compound of formula 2.6 wherein R62 is hydrogen, methoxy or ethoxy, R63 is hydrogen, methyl, methoxy or fluorine, R6 is COOMe, fluorine or chlorine, R65 is hydrogen or methyl, Y is methine, C-F or nitrogen, Z is methine or nitrogen, and R66 is fluorine or chlorine; and a compound of formula 2.7
wherein R6 is hydrogen or -C(O)-S-n-octyl; and a compound of formula 2.8
wherein R68 is either bromine or iodine; and a compound of formula 2.9
wherein R6g is chlorine or nitro; and a compound of formula 2.10 wherein R70 is fluorine or chlorine, and R71 is -CH2-CH(CI)-COOCH2CH3 or -NH-SO2Me; and a compound of formula 2.11
wherein R72 is trifluoromethyl or chlorine; and a compound of formula 2.12
wherein R73 is NH2 or <S>NH2; and a compound of formula 2.13
wherein Y2 is nitrogen, methine, C-NH-CHO, C-CH2-NH-SO2CH3 or N-Me, Y is nitrogen, methine, C-CI or C-l, Y3 is methine, Y4 is methine or Y3 and Y4 together are sulfur or C-CI, Y5 is nitrogen or methine, Y6 is methyl, difluoromethoxy, trifluoromethyl or methoxy, Y7 is methoxy or difluoromethoxy and R74 is CONMe2, COOMe, COOC2H5, trifluoromethyl, CH2-CH2CF3, O-CH2-CH2CI or SO2CH2CH3, or a sodium salt thereof; and the compound of formula 2.13.c and the compound of formula 2.14
and the compound of formula 2.15
and the compound of formula 2.16
HOOC N PO(OH)2 (2.16) and ammonium, isopropylammonium, sodium and
H trimesium salts thereof; and the compound of formula 2.17
and the compound of formula 2.18 and the compound of formula 2.19
and the compound of formula 2.20
and the compound of formula 2.21
and the compound of formula 2.22 and the compound of formula 2.23
and the compound of formula 2.24
n-pentyl
and the compound of formula 2.25
and the compound of formula 2.26
and the compound of formula 2.27
and the compound of formula 2.28 r- =\
Me— N JΠYJ ,N IN—— M iviee (2.28); cι- cι- and the compound of formula 2.29
and the compound of formula 2.30
and the compound of formula 2.31
and the compound of formula 2.32
and the compound of formula 2.33
HOOC I ( .V5όΛ),.
and the compound of formula 2.34
H2N - V- SO2NHCO2CH3 (2.34);
and the compound of formula 2.35
and the compound of formula 2.36
and the compound of formula 2.37 (2.37);
and the compound of formula 2.38 (2-38);
CH3
and the compound of formula 2.39 (2.39);
and the compound of formula 2.40 NHCON(CH3)2 (2.40);
CI — K - OC COpH , and the compound of formula 2.41 \ — / (2.41 );
CH3
and the compound of formula 2.42 H (2.42);
CH„
I 3
(CH3)3C -~ S . NCONHCH; and the compound of formula 2.43 N " N (2.43); and the compound of formula 2.44
and the compound of formula 2.45
and the compound of formula 2.46
and the compound of formula 2.47
and the compound of formula 2.48 and the compound of formula 2.49
and the compound of formula 2.50
and the compound of formula 2.51
and a compound of formula 2.52 wherein
R0i, R02 and R03 are each independently of the others halogen, nitro, cyano, C C4alkyl, C2-C4alkenyl, C2-C4alkynyl, d-C4haloalkyl, C2-C6haloaikenyl, C3-C6cycloalkyl, halo- substituted C3-C6cycloalkyl, CrC6alkoxyalkyl, CrC6alkylthioalkyl, hydroxy, mercapto, CrC6alkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, Cι-C alkylcarbonyl, d-C4alkoxycarbonyl, d-C4alkylthio, d-C4alkylsulfinyl, Cι-C4alkylsulfonyl, amino, d-C4alkylamino or di(d- C4alkyl)amino; R0 and R05 together are a group
-C-Ro6(Ro7)"O-C-Ro8(Ro9)-C-Roio(Ron)-C-Roi2(Roi3)- (Zi),
-C-Roι4(Roi5)-C-Roi6(Roi7)-O-C-Roι8(Roi9)-C-Ro2o(Ro2i)- (Z2) or
-C-Ro22(Rθ23)-C-Ro24(Rθ25)-C-Ro26(Rθ27)-O-C-Ro28(Rθ29)- (Z3), wherein RQ6, R07. Roe, R09, R010, Ron> Roi2> R013, Roι4> Roιs> Roιβ> R017. R018. Roi9> R020, R021, R022, R023, Ro24, R025, R026, R027, R028 and R029 are, each independently of the others, hydrogen, halogen, C C4alkyl or Cι-C4haloalkyl, it being possible for an alkylene ring, which together with the carbon atoms of the group Zi, Z2 or Z3 contains from 2 to 6 carbon atoms and which may be interrupted by oxygen, to be either fused or spiro-bound to the carbon atoms of the group Zi, Z2 or Z3 or that alkylene ring bridges at least one ring atom of the group Zι, Z2 or Z3;
G is hydrogen, -C(Xι)-R030, -C(X2)-X3-R03ι, -C(X4)-N(R032)-R033, -SO2-R034, an alkali metal cation, alkaline earth metal cation, sulfonium cation or ammonium cation or -P(Xs)(Ro3s)-Ro36; Xi, X2, X3, X and X5 are each independently of the others oxygen or sulfur; and R030, R031, R032, R033, Ro3 , Ro35 and Rose are each independently of the others hydrogen, CrC5alkyl, d-C5haloalkyl, C2-C5alkenyl, d-C5alkoxyalkyl, C3-C6cycloalkyl or phenyl, and Ro34 may additionally be C2-C20alkenyl; C2-C20alkenyl substituted by halogen, d- C6alkylcarbonyl, Cι-C6alkoxycarbonyl, CrC6alkylcarbonyIoxy, CrC6alkoxy, d-C6thioaIkyl, Cι-C6alkylthiocarbonyl, d-C6alkylcarbonylthio, Cι-C6alkylsulfonyl, CrC6alkylsulfoxyl, d- C6alkylaminosulfonyl, Cι-C6(di)alkylaminosulfonyl, Ci-CeCi-Cealkylsulfonyloxy, Cι-C6alkyl- sulfonylamino, d-C6alkylamino, CrC6(di)alkylamino, Cι-C6alkylcarbonylamino, di-d-C6 alkylcarbonylamino, d-C6alkylalkylcarbonylamino, cyano, (C3-C7)cycloalkyl, (C3- C7)heterocyclyl, tri-CrC6alkylsilyl, tri-Cι-C6alkylsilyloxy, phenyl or heteroaryl; or R034 is C2- C20alkynyl; C2-C20alkynyl substituted by halogen, Cι-C6alkylcarbonyl, d-C6 alkoxycarbonyl, CrC6alkylcarbonyloxy, CrC6alkoxy, Cι-C6thioalkyl, CrC6alkylthiocarbonyl, d- C6alkylcarbonylthio, CrC6alkyIsulfonyl, Cι-C6alkylsulfoxyl, Cι-C6aIkylaminosulfonyl, di-Cι-C6 alkylaminosulfonyl, CrC6alkylsulfonyloxy, Cι-C6alkylsulfonylamino, CrC6alkylamino, di- d- C6alkylamino, CrC6alkylcarbonylamino, di- CrC6alkylcarbonylamino, d- C6alkylcarbonylamino, cyano, (C3-C7)cycloalkyl, (C3-C7)heterocyclyl, tri-Cι-C6alkylsilyl, tri- C C6alkylsilyloxy, phenyl or heteroaryl; or R03 is (Cι-C7)cycloalkyl; (d-C7)cycloalkyl substituted by halogen, haloalkyl, d-C6alkyl, d-C6alkoxy, d-C6 alkylcarbonyloxy, C C6thioalkyl, d-C6alkylcarbonylthio, d-C6alkylamino, CrC6alkylcarbonylamino, tri- d- C6alkylsilyl or by tri- CrC6alkylsilyloxy; or R034 is heteroaryl; heteroaryl substituted by halogen, CrC6haloalkyl, nitro, cyano, CrC6alkyl, Cι-C6alkoxy, CrC6alkyIcarbonyloxy, d- C6thioalkyl, d-C6aIkylcarbonylthio, d-C6alkylamino, CrC6alkylcarbonylamino, tri- d- C6alkylsilyl or by tri- d-C6alkylsilyloxy; heteroaryloxy, heteroarylthio, heteroarylamino, di- heteroarylamino, phenylamino, diphenylamino, C2-C6cycloalkylamino, di-C2- C6cycloalkylamino or C2-C6cycloalkoxy and salts and diastereoisomers of compounds of formula 2.52; and the compound of formula 2.53
and the compounds prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P- ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlorotoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, trifluralin, fluthiamide, isoxaben, triallate, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin.
2. A method of controlling undesired plant growth in crops of useful plants, which comprises allowing a herbicidally effective amount of a composition according to claim 1 to act on the crop plant or the area of cultivation thereof.
3. A method according to claim 2, wherein the crop plant is maize or a cereal.
4. A method according to claim 2, wherein the crop of useful plants is treated with the said composition at a rate of application corresponding to a total amount of active ingredient of from 1 to 5000 g per hectare.
5. A selectively herbicidal composition that, in addition to comprising customary inert formulation adjuvants, such as carriers, solvents and wetting agents, comprises as active ingredient a mixture of a) an amount, effective for herbicide synergism, of the compound of formula I according to claim 1 and one or more compounds selected from the compounds of formulae 2.1 to 2.53 and the compounds prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P- ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlorotoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, trifluralin, fluthiamide, isoxaben, triallate, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin according to claim 1 and b) an amount, effective for herbicide antagonism, of a compound selected from the compound of formula 3.1 and the compound of formula 3.2
and the compound of formula 3.3
thereof or a hydrate or salt thereof, and the compound of formula 3.4
and the compound of formula 3.5
and the compound of formula 3.6 and the compound of formula 3.7
and the compound of formula 3.8
and of formula 3.9
CI2CHCON(CH2CH=CH2)2 (3.9),
and of formula 3.10
and of formula 3.11
and of formula 3.12
(3.12) or a methyl or ethyl ester thereof or a salt thereof,
and of formula 3.13
and of formula 3.14
and of formula 3.15
and of formula 3.16
H3C and of formula 3.17
6. A method for the selective control of weeds and grasses in crops of useful plants, which comprises treating the useful plants, seeds or cuttings thereof, or the area of cultivation thereof, with an amount, effective for herbicide synergism, of a composition according to claim 5.
7. A method according to claim 6, wherein the rate of application of herbicide is from 1 to 5000 g/ha and the rate of application of safener is from 0.001 to 0.5 kg/ha.
8. A method according to claim 6, wherein the crop of useful plants is maize or a cereal.
9. A selectively herbicidal composition that, in addition to comprising customary inert formulation adjuvants, such as carriers, solvents and wetting agents, comprises as active ingredient a mixture of a) a herbicidally effective amount of a compound of formula I according to claim 1 and b) an amount, effective for herbicide antagonism, of a compound selected from the compound of formula 3.1
and the compound of formula 3.2
and the compound of formula 3.3
thereof or a salt or hydrate thereof, and the compound of formula 3.4
and the compound of formula 3.5
and the compound of formula 3.6
and the compound of formula 3.7
and the compound of formula 3.8
and of formula 3.9
CI2CHCON(CH2CH=CH2)2 (3.9),
and of formula 3.10 and of formula 3.11
and of formula 3.12
(3.12) or a methyl or ethyl ester thereof or a salt thereof,
and of formula 3.13
and of formula 3.14 and of formula 3.15
and of formula 3.16
H3C and of formula 3.17
10. A method for the selective control of weeds and grasses in crops of useful plants, which comprises treating the useful plants, seeds or cuttings thereof, or the area of cultivation thereof, with a selective herbicidal amount of a composition according to claim 9.
EP02796559A 2001-12-03 2002-12-02 Herbicidal composition Withdrawn EP1450607A1 (en)

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AR071339A1 (en) * 2008-02-05 2010-06-16 Arysta Lifescience North Ameri SOLID FORMULATION OF LOW FUSION ACTIVE COMPOUND
WO2009102689A2 (en) * 2008-02-12 2009-08-20 Arysta Lifescience North America, Llc Method of controlling unwanted vegetation
GB0810554D0 (en) * 2008-06-09 2008-07-16 Syngenta Ltd Herbicde composition
PT3120702T (en) 2009-10-28 2019-03-19 Dow Agrosciences Llc Synergistic herbicidal composition containing fluroxypyr and profoxydim
US20140128262A1 (en) * 2012-11-05 2014-05-08 Valent U.S.A. Corporation Compositions and Methods for Residual Weed Control With PPO Inhibitors and Gibberellic Acid
CN114503991A (en) * 2022-03-01 2022-05-17 陕西上格之路生物科学有限公司 Weeding composition containing fluopicolide

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